Polyamino-polyamide crosslinked with crosslinking agent

ABSTRACT

A cosmetic composition for the hair comprises at least one water-soluble crosslinked polymer obtained by crosslinking a polyamino-polyamide with a crosslinking agent, said polyamino-polyamide being prepared by the polycondensation of (a) an acidic compound selected from the group consisting of (i) organic dicarboxylic acid, (ii) ethylenically unsaturated aliphatic mono- or di-carboxylic acid, (iii) ester of said acids of (i) and (ii), and (iv) mixtures of (i), (ii) and (iii) on (b) a polyamine selected from the group consisting of bis-primary and mono- and bis-secondary polyalkylene polyamines, said polyamine (b) being replaceable by a member selected from the group consisting of (1) 0-20 mole percent hexamethylene diamine, (2) 0-40 mole percent bis-primary amine and (3) 0-40 mole percent bis-secondary amine, said crosslinking agent being selected from the group consisting of (a&#39;) simple bi-functional compounds selected from bis-halohydrins, bis-azetidinium, bis-haloacyl diamine and alkyl bis-halides, (b&#39;) oligomers obtained by the reaction of (1&#39;) a compound selected from the group consisting of the compounds in (a&#39;) above or an epihalohydrin,a bis-epoxide, or a bis-unsaturated derivative with (2&#39;) a compound reactive with the compound in (1&#39;), and (c&#39;) the quaternized compounds comprising said crosslinked polymer alkylated with an alkylating agent selected from the group consisting of (a) epoxides, (b) ethylenically unsaturated compounds, (c) chloroacetic acid, and (d) alkane sultone selected from the group consisting of propane sultone and butane sultone. The crosslinking agent is employed in amounts of 0.025-0.35 mole per amine group in said polyamino-polyamide. The said crosslinked polymer is soluble in water in amounts of 10 weight percent thereof without essentially any gel formation and a 10 weight percent aqueous solution of the said crosslinked polymer has a viscosity greater than 3 centipoises at 25° C.

This application is a division of our application Ser. No. 881,513,filed Feb. 2, 1978, now U.S. Pat. No. 4,189,468, which is acontinuation-in-part of application Ser. No. 762,804, filed Jan. 26,1977, now U.S. Pat. No. 4,172,887, which is a continuation ofapplication Ser. No. 528,577, filed Nov. 29, 1974, now abandoned.

BACKGROUND OF THE INVENTION

It is known that the hair of many people, because of its generalcondition or because of repeated exposure to the atmosphere or totreatments such as bleachings, permanent wavings or dyeings, becomesdegraded and often difficult to comb out or to set, especially in thecase of a thick head of hair which is often dry, dull, rough or lacksvigor and liveliness.

Efforts heretofore have been made to limit or to correct these faults byapplying to the hair a "hair conditioner" composition so as to improvethe condition of moist and dry hair and to facilitate such operations ascombing and setting the hair.

By "Hair conditioning" is meant an operation which, while facilitatingthe combing out of moist hair, also imparts to dry hair some swellingand elasticity, so as to assure good maintenance of the coiffure orstyle imparted thereto. The agents employed to achieve such "hairconditioning" are generally called "hair conditioners".

Conventionally there are employed in the conditioning of hair varioussynthetic polymers, such as polyethylene imines, polyvinylpyridines, thepolychloride of p-vinylbenzyl trimethylammonium and the polychloride ofdiallyl dimethyl ammonium. However, it has also been found that thesepolymers suffer from the disadvantages of not being compatible with, forinstance, anionic shampoo compositions.

It has also been known to use in the production of compositions for hairsome polyamino-amide polymers, obtained by the polycondensation of adicarboxylic acid and a polyalkylene polyamine, some polyaminoureylenepolymers and some alkylene polyamine polymers modified particularly byepichlorohydrin in quantities near stoichiometric amounts relative tothe amine groups of the polyamino-amide. However, the addition of thesesignificant quantities of epichlorohydrin leads to the presence in themolecules of the crosslinked polymer some reactive groups. Thesepolymers thus contain alkylating groups which are capable of reacting onnucleophilic groups such as amines, thiols, sulfates and the like.Representative of such alkylating groups are azetidinium rings. However,as a result of the presence of such reactive groups, the polymer lacksstability and generally degrades when put into solution. Further thepresence of such alkylating groups renders cosmetic productsincorporating the same of doubtful use for application to human skin.

There has also been recommended the use in a "hair conditioner"composition of heat crosslinkable thermosetting polymers, but their usenecessarily involves a special heating step.

To avoid these drawbacks, there has been provided in our earlierapplications Ser. Nos. 762,804 and 528,577, incorporated herein byreference, a chemically stable, crosslinked polyamino-polyamide freefrom reactive groups. This water-soluble crosslinked polymer is obtainedby crosslinking a polyamino-polyamide which in turn is prepared by thepolycondensation of an acidic compound on a polyamine. The acidiccompound used is selected from the group consisting of:

(i) an organic dicarboxylic acid,

(ii) an ethylenically unsaturated aliphatic mono- or di-carboxylic acid,

(iii) an ester of said acids, preferably with a lower alkanol havingfrom 1-6 carbon atoms, and

(iv) mixtures of these compounds.

The polyamine usefully employed to produce the polyamino-polyamide ofour earlier applications is selected from the group consisting ofbis-primary and mono- or bis-secondary polyalkylene-polyamines. From0-40 mole percent of the selected polyamine can be replaced by abis-primary amine, preferably, ethylenediamine or by a bis-secondaryamine, preferably piperazine and 0-20 mole percent of the selectedpolyamine can be replaced by hexamethylene-diamine.

Crosslinking of the polyamino-polyamide in our earlier applications iseffected with a crosslinking agent selected from the group consisting ofepihalohydrins, diepoxides, dianhydrides, unsaturated anhydride and bisunsaturated derivatives, and is characterized by the fact that thecrosslinking agent is employed in amounts of 0.025-0.35 mole ofcrosslinking agent per amine group of the polyamino-polyamide andgenerally from 0.025 up to about 0.2 mole and, in particular, from 0.025to up to about 0.1 mole of crosslinking agent per amine group of thepolyamino-polyamide.

Our earlier invention, as described in said Ser. Nos. 762,804 and528,577 is also concerned with a hair conditioning cosmetic compositionwhich comprises at least one water-soluble crosslinked polymer asdefined above. This cosmetic composition is compatible with anionicshampoo compositions; it provides satisfactory combing out of moist hairand it imparts elasticity to dry hair thereby assuring good maintenanceof the coiffure or style imparted to the hair.

The crosslinked polyamino-polyamidde present in the hair conditioningcomposition of our earlier invention exhibits the followingcharacteristics: (1) it is perfectly soluble in water up to 10 waterpercent concentration without forming a gel; (2) the viscosity of such a10% solution in water at 25° C. is greater than 3 centipoises, theviscosity generally measuring between 3-200. More often the viscosity ofsuch a solution is equal to or greater than 20 centipoises and lowerthan 50 centipoises; and (3) the polyamino-polyamide does not carry anyreactive group and in particular it is chemically stable and does nothave any alkylating characteristics.

DESCRIPTION OF THE INVENTION

The present invention is an improvement over our invention disclosed insaid Ser. Nos. 762,804 and 528,577. Thus, it has now been found that byusing different crosslinking agents, new crosslinked polyamino-polyamidepolymers, as well as new cosmetic compositions for the hair containingthese new polymers have now been provided.

In accordance with the present invention, the new polymers and the newcompositions containing them exhibit relative to the polymers and to thehair compositions described in our earlier applications the advantage ofimparting to the hair a better cosmetic state and principally ofimpartingto dry hair more body and elasticity, and improving orprolonging the maintenance of the hair style.

This advantage is more significant in the case of damaged hair havingbeen submitted to successive bleachings and/or permanent wavetreatments.

The new crosslinking agents employed in the present invention can beclassified into the following three groups:

I--Simple bi-functional compounds selected from the group consisting ofbis-halohydrins, bis-azetidinium, bis-haloacyl diamines and bis-alkylhalides;

II--Oligomers obtained by the reaction of compound (a) selected from thegroup consisting of the bi-functional compounds described in Group Iaboveand the bi-functional crosslinking agents described in our earlierapplications, i.e. epihalohydrins, bis-epoxides and bis-unsaturatedderivatives, and specifically epichlorohydrin, N,N'-bis-epoxy propylpiperazine, diglycidyl ether, divinyl sulfone, methylene bis-acrylamide,on compound (b) which is a bi-functional compound reactive with compound(a);

III--The product of quaternization of a compound selected from the groupconsisting of compounds (a), described in the preceding paragraph, andtheoligomers described in Group II which carry one or more tertiaryamine groups totally or partially alkylatable with a known alkylatingagent and in particular with an alkylating agent selected from the groupconsisting of chlorides, bromides, iodides, sulfates, mesylates andtosylates of methyl or ethyl, benzyl chloride or bromide, ethyleneoxide, propylene oxide and glycidol.

More preferably the polymers of the present invention are produced usinga crosslinking agent selected from the group consisting of

(I) simple bi-functional compounds selected from the group consisting of(1) bis-halohydrins resulting from the reaction of epihalohydrin with aprimary amine, a bis-secondary diamine, a bis-phenol, or abis-mercaptan, (2) bis-azetidinium, (3) bis-haloacyl diamines, (4) alkylbis-halides of the formula ##STR1##where X=Cl or Br, Z represents##STR2##x=1 to 3, m=0 or 1, n=0 or 1, m and n not representing 1 at thesame time; moreover, when m=1, x=1; A₁ represents a saturated divalenthydrocarbon radical having 2, 3, 4 or 6 carbon atoms or 2-hydroxypropylene;

(II) oligomers obtained by the reaction of compound (a) selected fromthe group consisting of compounds (1), (2), (3) and (4), each identifiedabove, (5) epihalohydrins, (6) bis-epoxides and (7) bis-unsaturatedderivatives with compound (b) which is a bi-functional compound reactivewith compound (a) and selected from the group consisting of primaryamines, bis-secondary diamines, bis-mercaptans and bis-phenols; themolar ratio of (b):(a) being between 0.1 and 0.9;

(II-bis) oligomers obtained by the reaction of compound (a₁) selectedfrom the group consisting of compounds (1), (3), (4) and (6) eachidentified above with a bis-tertiary diamine (b₁) which is abi-functional compound reactive with compound (a₁); the molar ratio(b₁):(a₁) being between 0.1 and 0.9;

(III) the product of quaternization of a compound (a₂) selected from thegroup consisting of (1) bis-halohydrins resulting from the reaction ofaepihalohydrin with piperazine, a bis-phenol or a bis-mercaptan, (2)bis-azetidinium, (3) bis-haloacyl diamines, (4) alkyl bis-halides offormula F₁, above, (6) bis-epoxides, (7) bis-unsaturated derivatives,(8)oligomers of II above, obtained by the reaction of compound (a₃)selected from the group consisting of compounds (1), (2), (3), (4), (6)and (7) each identified above with compound (b₃) which is abi-functional compound reactive with compound (a₃) and selected from thegroup consisting of primary amines, bis-secondary diamines,bis-mercaptans and bis-phenols, the molar ratio (b₃):(a₃) being between0.1 and 0.9, (9) oligomers obtained by the reaction of an epihalohydrin(compound a₄) with a bi-functional compound (b₄) selected frompiperazine, bis-mercaptans, bis-phenols and bis-epoxides of piperazine,the molar ratio of (b₄):(a₄) being between 0.1 and 0.9; (10) oligomersobtained by the reaction of compound (a₅) selected from the groupconsisting of (1) bis-halohydrins resulting from the reaction of anepihalohydrin with piperazine, a bis-phenol or a bis-mercaptan, (2)bis-haloacyl diamines, (3) alkyl bis-halides of formulaF₁, above, and(4) bis-epoxides, with compound (b₅) which is a bis-tertiary diamine,the molar ratio (b₅):(a₅) being between 0.1 and 0.9; the said producthaving at least one tertiary amine group which is alkylatable, with analkylating agent (c) selected from the groupconsisting of chlorides,bromides, iodides, sulfates, mesylates and tosylates of methyl or ethyl,benzyl chloride or bromide, ethylene oxide, propylene oxide andglycidol.

The simple bi-functional compounds of Group I are more specifically:

(1') bis-halohydrins obtained by the reaction of an epihalohydrin, suchas epichlorohydrin or epibromohydrin with a bi-functional compound suchas bis-secondary diamines, primary amines, diols, bis-phenols orbis-mercaptans. These bis-halohydrins form very valuable crosslinkingagents.

The bis-halohydrin resulting from the reaction of epichlorohydrin withpiperazine is particularly valuable.

The bis-halohydrins can be direct intermediates for the preparation ofbis-epoxides, but, inversely, they can be derived by opening the oxiranering with an hydracid such as hydrochloric acid or hydrobromic acid.

In both cases, the halogen atom can be linked at the last carbon atom orthe next-to-last carbon atom without its position being prejudicial tothereactivity of the crosslinking agent or to the properties of thefinal product.

Representative useful bis-halohydrins include the following: ##STR3##andin formulas (1)-(7), X represents Cl or Br.

(2') bis-azetidinium compounds derived from N,N-dialkyl halogeno hydroxypropylamines by cyclization. A representative bis-azetidinium is onemade in accordance with the following reaction scheme: ##STR4##wherein Xrepresents Cl or Br.

However, the cyclization can be difficult for certain stericallyhindered amines.

As the reactivity of the azetidinium groups is only slightly differentfromthat of epihalohydrin groups, there can be employed in the presentinvention compounds derived from bis-halohydrins for which thehalohydrin units are linked to the remainder of the molecule by tertiarynitrogen groups, and carry two azetidinium groups or one azetidiniumgroup and one halohydrin group;

(3') bis-haloacyl diamines useful as crosslinking agents can berepresentedby the formula: ##STR5##wherein X=Cl or Br, A=--CH₂ --CH₂ --,--CH₂ --CH₂ --CH₂ -- or ##STR6##n represents a number between 1 and 10,R₁ =R₂ =H or R₁ and R₂ can be linked together and represent an ethyleneradical; when ##STR7##R₁ =R₂ =H; when A represents --CH₂ --CH₂ --, R₁and R₂ can be linked together and represent ethylene so that the group##STR8##designates the radical ##STR9##which can be derived frompiperazine.

Particularly useful bis-haloacyl diamines in the invention are thebis-chloroacetyl or the bis-bromo undecanoyl of ethylenediamine or ofpiperazine.

Particularly useful bis-epoxides are bis-epoxides of piperazine;

(4') oligomers, within the meaning of the present invention, arestatistical mixtures of compounds obtained by the reaction of compound(a)described in Groups I and II or of a compound (a₁) described in GroupII-bis or of a compound (a₃), (a₄) or (a₅) described in Group III with,respectively, a bi-functional compound (b), (b₁), (b₃), (b₄), (b₅) whichare reactive with compounds (a), (a₁), (a₃), (a₄), (a₅) which are in ageneral fashion,primary amines, bis-secondary amines such as piperazine,bis-tertiary diamines such as N,N,N',N'-tetramethyl ethylene-,propylene-, butylene-, or hexamethylene-diamine, bis-mercaptans such asethane 1,2-dithiol, or the bis-phenols such as Bis-phenol A or2,2'-(4,4'-dihydroxy-diphenyl) propane.

The molar amount of (b), (b₁), (b₃), (b₄) and (b₅), relative,respectively, to (a), (a₁), (a₃), (a₄) and (a₅) is between 0.1 and 0.9.

The oligomerization reaction is generally carried out at temperaturesbetween 0° and 95° C. and preferably between 0° and 50° C. in water, orin a solvent such as isopropanol, t-butanol, acetone, benzene, toluene,dimethylformamide or chloroform.

The quaternization reaction which provides the quaternization productdescribed above, under III, is effected between 0° and 90° C. in wateror in a solvent such as methanol, ethanol, isopropanol, t-butanol,alkoxy ethanols, acetone, benzene, toluene, dimethylformamide orchloroform.

Thus, the present invention relates to a crosslinked polyamino-polyamidepolymer prepared by crosslinking a polyamino-polyamide, obtained by thepolycondensation of an acidic compound selected from (i) organicdicarboxylic acids, (ii) aliphatic ethylenically unsaturated mono- anddi-carboxylic acids, (iii) the esters of the said acids and (iv)mixtures of these compounds, on a polyamine selected from bis-primaryand mono- or di-secondary polyalkylene-polyamines, 0 to 20 mole percentof this polyamine being able to be replaced by hexamethylene diamine, or0 to 40 percent of this polyamine being able to be replaced by abis-primary amine, preferably, ethylene diamine, or by a bis-secondaryamine, preferably, piperazine. The crosslinking is effected using acrosslinking agent selected from the group consisting of:

(I) simple bi-functional compounds selected from the group consisting of(1) bis-halohydrins resulting from the reaction of an epihalohydrin withaprimary amine, a bis-secondary diamine, a bis-phenol or a bis-mercaptan(2)bis-azetidinium, (3) bis-haloacyl diamines, (4) alkyl bis-halidesrepresented by the formula: ##STR10##wherein X=Cl or Br, Z represents##STR11##x=1 to 3, m=0 or 1, n=0 or 1, m and n at the same time notrepresenting 1; moreover when m=1, x=1; A₁ represents a divalentsaturated hydrocarbon having 2, 3, 4 or 6 carbon atoms or 2-hydroxypropylene;

(II) oligomers obtained by the reaction of compound (a) selected fromthe group consisting of compounds (1), (2), (3) and (4), each identifiedabove, (5) epihalohydrins, (6) bis-epoxides and (7) bis-unsaturatedderivatives; with compound (b) which is a bi-functional compoundreactive with compound (a) and selected from the group consisting ofprimary amines, bis-secondary amines, bis-mercaptans and bis-phenols;

(II-bis) oligomers obtained by the reaction of compound (a₁) selectedfrom the group consisting of compounds (1), (3), (4) and (6) eachidentified above with a bis-tertiary diamine (b₁) which is abi-functional compound reactive with compound (a₁); the molar ratio(b₁):(a₁) being between 0.1 and 0.9;

(III) the product of quaternization of compound (a₂) selected fromthegroup consisting of (1) bis-halohydrins resulting from the reactionof an epihalohydrin with piperazine, a bis-phenol or a bis-mercaptan,(2) bis-azetidinium, (3) bis-haloacyl diamines, (4) alkyl bis-halides offormula F₁, (6) bis-epoxides, (7) bis-unsaturated derivatives, (8)oligomers II obtained by the reaction of compound (a₃) selected from thegroup consisting of compounds (1), (2), (3), (4), (6) and (7) eachidentified above with compound (b₃) which is a bi-functionalcompoundreactive with compound (a₃) and selected from the groupconsisting of primary amines, bis-secondary diamines, bis-mercaptans andbis-phenols, the molar ratio (b₃):(a₃) being between 0.1 and 0.9, (9)oligomers obtained by the reaction of an epihalohydrin (compound a₄)with a bi-functional compound (b₄) selected from piperazine,bis-mercaptans, bis-phenols, bis-epoxides of piperazine; the molar ratioof (b₄):(a₄) being between 0.1 and 0.9; (10) oligomers obtained by thereaction of a compound (a₅) selected from the group consistingof (1)bis-halohydrins resulting from the reaction of an epihalohydrinwithpiperazine, a bis-phenol or a bis-mercaptan, (2) bis-haloacyldiamines, (3)alkyl bis-halides of formula F₁ and (4) bis-epoxides withcompound (b₅) which is a bis-tertiary diamine, the molar ratio (b₅):(a₅)being between 0.1 and 0.9; said product having at least one tertiaryamine group alkylatable with an alkylating agent (c) selected from thegroup consisting of chlorides, bromides, iodides, sulfates, mesylatesand tosylates of methyl or ethyl, benzyl chloride or bromide, ethyleneoxide, propylene oxide and glycidol.

The acids useful for the preparation of the polyamino-polyamide of thepresent invention are selected from organic saturated dicarboxylic acidshaving from 6 to 10 carbon atoms, for example adipic acid,2,2,4-trimethyland 2,4,4-trimethyl adipic acids; terephthalic acid;aliphatic ethylenically unsaturated mono- and di-carboxylic acids, forexample, acrylic acid, methacrylic acid and itaconic acid.

Among the preferred acids are adipic acid and the addition compounds ofan alkylene diamine with an unsaturated acid such as acrylic acid,methacrylic acid and itaconic acid.

Adipic acid is particularly preferable.

The esters of the above mentioned acids can also be used. It is alsopossible to use mixtures of two or more carboxylic acids and theiresters.

The polyamines useful for the preparation of the polyamino-polyamide ofthepresent invention are selected from bis-primary and mono- ordi-secondary polyalkylene-polyamines, for example, diethylene triamine,dipropylene triamine, triethylene tetramine and their mixtures.

The polycondensation is carried out in accordance with known procedures,bymixing the initial reactants; heating the resulting mixture to atemperature between 80° and 250° C., and preferably between 100° and180° C., for 1 to 8 hours. The choice of the exact reaction time andtemperature can depend on the choice of the particular reactantsselected but the same is easily determined by those skilled in the art.After heating the reaction mixture at total reflux for 1/2 hour to 1hour, the water or alcohol formed during the course of thepolycondensation is removed at first at atmospheric pressure and then atsubatmospheric pressure.

The polycondensation reaction is carried out under a nitrogen atmospheretoavoid any significant colorations and to facilitate the elimination ofvolatile substances.

In carrying out the polycondensation reaction preferably equimolaramounts of the dicarboxylic acid and amine are employed.

According to a preferred embodiment of the present invention, thepolycondensation of the polyalkylene-polyamine selected preferably fromdiethylene triamine, triethylene tetramine, dipropylene triamine andmixtures thereof is effected with either (i) a carboxylic diacid,preferably adipic acid or its dimethyl ester, or (ii) the intermediateproduct of addition of one molecule of ethylene diamine and twomolecules of the methyl ester of an ethylenically unsaturated acid suchas methyl acrylate or methyl itaconate.

The addition reaction of ethylene diamine on the said unsaturated esteris carried out by mixing the reactants at a temperature between 5°-80°C. The polycondensation reaction is effected by heating the reactantsfor 30-60 minutes at reflux followed by eliminating the methyl alcoholformed, at a temperature of 120°-150° C.,or of the water formed at atemperature of 140°-175° C., initially under atmospheric pressure andfinally under sub-atmospheric pressure of 15 mm of mercury.

The polyamino-polyamides (A) thus obtained have a viscosity in a 10%aqueous solution at 25° C. lower than 3 centipoises.

The preferred polyamino-polyamides (A) of the present invention arecharacterized by repeating units of the formula

    --OC--R--CO--Z--                                           (I)

wherein R represents a bivalent radical which is derived from the acidemployed or from the addition product of the acid with a bis-primary orbis-secondary amine.

Representative preferred values for R includes ##STR12##

These radicals are derived, respectively, from terephthalic acid, adipicacid, the product of addition of ethylenediamine with acrylic acid,methacrylic acid and itaconic acid, or their esters;

Z is selected from the group consisting of:

(1) in amounts of 60-100 mole percent, the radical

    --NH--(CH.sub.2).sub.x --NH].sub.n                         (III)

wherein (a) x=2 and n=2 or 3 or (b) x=3 and n=2, this radical beingderivedfrom diethylene triamine, triethylene tetramine or dipropylenetriamine;

(2) in amounts of 0-40 mole percent (a) the radical (II) above, in whichx=2 and n=1, the said radical being derived from ethylenediamine, or (b)the radical ##STR13##which is derived from piperazine; and

(3) in amounts of 0-20 mole percent the radical --NH--(CH₂)₆ --NH--which is derived from hexamethylenediamine.

The polyamino-polyamides thus obtained are then crosslinked by theadditionof a crosslinking agent selected from those described above.

The crosslinking reaction is effected at a temperature between 20° C.and 90°0 C. using initially 20 to 30% aqueous solutions of thepolyamino-polyamide to which is added the crosslinking agent by verysmallfractions until there is obtained a significant increase in theviscosity, but without, however, forming a gel which no longer issoluble in water. The concentration is then rapidly adjusted to 10% bythe addition of waterand the reaction mixture is then cooled.

According to a preferred characteristic of the present invention, thereis employed during the crosslinking of the polyamino-polyamide polymers,a crosslinking agent in amounts of 0.025 to 0.35 mole per amine group ofthepolyamino-polyamide. An interesting category of crosslinked polymersis obtained by using from 0.025 to up to about 0.2 mole of crosslinkingagentper amine group of the polyamino-polyamide. Another advantageouscategory of crosslinked polymers is obtained by using from 0.025 to upto about 0.1mole of crosslinking agent per amine group of thepolyamino-polyamide.

The amount of crosslinking agent to use, which can vary according to thenature of the polyamino-polyamide and of the crosslinking agent can beeasily determined by adding the desired crosslinking agent to an aqueoussolution of the polyamino-polyamide until the viscosity of a 10%solution is at 25° C. between 3 centipoises and the gel state whilepreserving its perfect solubility in water.

The crosslinked polymers according to the present invention keep welland are compatible with anionic surfactants while providing gooduntangling ofwet hair. This compatibility with anionic surfactants canagain be improvedby alkylation of the secondary amine groups of thecrosslinked polyamino-polyamides. The alkylation improves the watersolubility of the crosslinked polyamino-polyamides, in the presence ofanionic surfactants.

The following alkylating agents can be employed:

(1) an epoxide, for example, glycidol, ethylene oxide, or propyleneoxide,

(2) an ethylenically unsaturated compound, for example, acrylamide andacrylic acid;

(3) chloroacetic acid; and

(4) an alkane sultone, for example, propane sultone or butane sultone.

The alkylation of the crosslinked polyamino-amides is carried out in anaqueous solution, at a concentration of 10 to 30% and at a temperaturebetween 10° and 95° C.

The crosslinked polymers according to the present invention can be usedin various cosmetic compositions for the hair, for the treatment ofnormal hair and more particularly for the treatment of sensitized hair.They can also be used in concentrations from 0.1 to 5 weight percent,preferably, from 0.2 to 2.5 weight percent and advantageously, from 0.3to 1.3 weight percent in cosmetic compositions for the hair and moreparticularly in shampoo compositions, such as an anionic, cationic,non-ionic, amphoteric or zwitterionic shampoo composition, a shampoo-dyecomposition, a hair dyecomposition, a hair styling gel, a hair stylinglotion, a "brushing" lotion, a hair setting lotion, a hair rinse lotion,a non-rinse hair reinforcing setting lotion, a hair restructuringlotion, and in such cosmetic compositions as anti-pellicular andanti-seborrheic compositions and permanent waving compositions.

The present invention thus also relates to a cosmetic composition forthe hair containing at least one water-soluble crosslinked polymerobtained bycrosslinking a polyamino-polyamide prepared by thepolycondensation of an acid compound selected from (i) organicdicarboxylic acids, (ii) aliphaticethylenically unsaturated mono- anddi-carboxylic acids, (iii) esters of the said acids and (iv) mixtures ofthese compounds, on a polyamine selected from bis-primary and mono- ordi-secondary polyalkylene-polyamines, 0 to 20 mole percent of thispolyamine being ableto be replaced by hexamethylene diamine, or 0 to 40percent of this polyamine being able to be replaced by a bis-primaryamine, preferably, ethylene diamine or by a bis-secondary amine,preferably, piperazine; the crosslinking being carried out with the useof a crosslinking agent selected from the group consisting of

(I) a compound selected from the group consisting of (1)bis-halohydrins, (2) bis-azetidinium, (3) bis-haloacyl diamines and (4)alkyl bis-halides;

(II) oligomers obtained by the reaction of compound (a) selected fromthe group consisting of (1) bis-halohydrins, (2) bis-azetidinium, (3)bis-haloacyl diamines, (4) alkyl bis-halides, (5) epihalohydrins, (6)bis-epoxides and (7) bis unsaturated derivatives, with compound (b)which is a bi-functional compound reactive with compound (a);

(III) the product of quaternization of a compound selected from thegroup consisting of compound (a) and oligomers (II) and carryingtertiary amine groups alkylatable with an alkylating agent (c) selectedfrom the group consisting of the chlorides, bromides, iodides, sulfates,mesylates and tosylates of methyl or ethyl, benzyl chloride or bromide,ethylene oxide, propylene oxide and glycidol.

The crosslinking is advantageously carried out by means of acrosslinking agent selected from the group consisting of:

(I) simple bi-functional compounds selected from the group consisting of(1) bis-halohydrins resulting from the reaction of an epihalohydrin withaprimary amine, a bis-secondary amine, a bis-phenol or a bis-mercaptan,(2) bis-azetidinium, (3) a bis-haloacyl diamine, (4) an alkyl bis-halidehaving the formula ##STR14##wherein X=Cl or Br, Z represents##STR15##x=1 to 3, m=0 or 1, n=0 or 1, m and n not representing 1 at thesame time; moreover, when m=1, x=1; A₁ represents a saturated divalenthydrocarbon radical having 2, 3, 4 or 6 carbon atoms or 2-hydroxypropylene;

(II) oligomers obtained by the reaction of compound (a) selected fromthe group consisting of compounds (1), (2), (3) and (4) each identifiedabove,(5) epihalohydrins, (6) bis-epoxides and (7) bis-unsaturatedderivatives with compound (b) which is a bi-functional compound reactivewith compound(a) and selected from the group consisting of primaryamines, bis-secondarydiamines, bis-mercaptans and bis-phenols; the molarratio (b):(a) being between 0.1 and 0.9;

(II-bis) oligomers obtained by the reaction of compound (a₁) selectedfrom the group consisting of compounds (1), (3), (4), and (6) eachidentified above with a bis-tertiary diamine (b₁) which is abi-functional compound reactive with compound (a₁); the molar ratio(b₁):(a₁) being between 0.1 and 0.9;

(III) the product of quaternization of compound (a₂) selected fromthegroup consisting of (1) bis-halohydrins resulting from the reactionof an epihalohydrin with piperazine; bis-phenols or bis-mercaptans, (2)bis-azetidinium, (3) bis-haloacyl diamines, (4) alkyl bis-halides offormula F₁ above, (6) bis-epoxides, (7) bis-unsaturated derivatives, (8)oligomers II obtained by the reaction of compound (a₃) selected from thegroup consisting of compounds (1), (2), (3), (4), (6), and (7) eachidentified above with compound (b₃) which is a bi-functional compoundreactive with compound (a₃) and is selected from the group consisting ofprimary amines, bis-secondary diamines, bis-mercaptans and bis-phenols,the molar ratio (b₃):(a₃) being between 0.1 and 0.9, (9) oligomersobtained by the reaction of an epihalohydrin (compound a₄) with abi-functional compound (b₄) selected from piperazine,bis-mercaptans,bis-phenols and bis-epoxides of piperazine, the molar ratioof (b₄):(a₄)being between 0.1 and 0.9; (10) oligomers obtained by the reaction ofcompound (a₅) selected from the group consisting of (1) bis-halohydrinsresulting from the reaction of an epihalohydrin with piperazine, abis-phenol or a bis-mercaptan, (2) bis-haloacyl diamines, (3) alkylbis-halides of formula F₁ above, and (4) bis-epoxides, with compound(b₅) which is a bis-tertiary diamine, themolar ratio (b₅):(a₅) beingbetween 0.1 and 0.9; said product carrying tertiary amine groupsalkylatable with an alkylating agent (c) selected from the groupconsisting of the chlorides, bromides, iodides, sulfates, mesylates andtosylates of methyl or ethyl, benzyl chloride or bromide, ethyleneoxide, propylene oxide and glycidol.

The cosmetic composition is characterized by the fact that thepolyamino-polyamide is crosslinked by means of 0.025 to 0.35, or betterfrom 0.025 to about 0.2, or even better from 0.025 to about 0.1 mole ofcrosslinking agent per amine group of the polyamino-polyamide. Thecrosslinked polymer in the cosmetic composition of the present inventionexhibits a combination of the following characteristics:

(1) it is perfectly soluble in water at 10% without formation of a gel;

(2) the viscosity of a 10% solution of polymer in water at 25° C.isgreater than 3 centipoises; and

(3) it does not have any reactive groups and in particular it does nothaveany alkylating properties and it is chemically stable.

The cosmetic compositions for the hair containing the crosslinkedpolymer of the present invention can have a pH between 2 and 11 andpreferably between 3 and 8.

The cosmetic compositions for the hair according to the presentinvention before being applied to sensitized hair can include,advantageously, an electrolyte. The presence of the electrolyte in thecomposition reduces orsuppresses the tendency sensitized hair has to fixdurably the polymers. Representative useful electrolytes includewater-soluble alkali or alkaline earth salts of mineral or organic acidsand preferably the chlorides and acetates of sodium, potassium, ammoniumand calcium. The amount of electrolyte is not critical. Preferably theelectrolyte is present in an amount between 0.01 and 5 weight percentand advantageously from 0.4 to 3 weight percent of the total weight ofthe composition. The ratio of electrolyte:polymer is between 0:1 and1.5:1.

The cosmetic compositions for the hair can be colored and thus containfrom0.001 to 0.5 weight percent of a dye based on the total weight ofthe composition. The cosmetic composition also conventionally contains aperfume in an amount of 0.1 to 0.5 percent by weight based on the totalweight of the composition.

In the compositions of the present invention, the crosslinkedpolyamino-polyamide is present in an amount of 0.1 to 5 weight percentandpreferably 0.1 to 3 weight percent based on the total weight of thecomposition.

The cosmetic compositions for the hair in accordance with the presentinvention can be provided in the form of aqueous or alcoholic solutions,the alcohol being a lower alkanol such as ethanol or isopropanol, or inthe form of a cream, a gel, a dispersion, or an emulsion.

In addition to the crosslinked polyamino-polyamide, the cosmeticcomposition can include, generally, various adjuvants conventionallyemployed in cosmetic compositions for the hair. The adjuvants generallypresent in these cosmetic compositions are, for example, perfumes, dyes,preservatives, sequesterants, thickening agents, emulsifiers, anionic,cationic, amphoteric, zwitterionic or non-ionic surfactants, synergists,softening agents, cosmetic polymers or resins and in particularnon-ionic or cationic polymers or resins.

The cosmetic compositions for the hair, according to the presentinvention,constitute principally treating creams to be applied to thehair before or after dyeing or bleaching the same, before or aftershampooing the hair, before or after a permanent waving of the hair;hair dye products; shampoos; rinse lotions to be applied before or aftera shampoo; hair setting lotions; brushing lotions; and hair structuringlotions.

When the compositions of the present invention constitute a treatingcream to be applied before or after dyeing or bleaching the hair, beforeor after shampooing the hair, before or after a permanent waving of thehair,the carriers for these creams are formulated from soaps or a fattyalcohol in the presence of emulsifiers. They can also contain fattyamides, glycerine, polymers, perfumes and dyes.

The pH of these creams is between 3 and 9 and preferably between 5 and9.

The soaps can be constituted from natural or synthetic fatty acidshaving 12-18 carbon atoms, such as lauric acid, myristic acid, palmiticacid, oleic acid, ricinoleic acid, stearic acid and isostearic acid, inconcentrations between 10 and 30% and alkalizing agents such as NaOH,KOH,ammonia, monoethanolamine, diethanolamine and triethanolamine.

Representative fatty amides include, in particular, the followingcompounds: mono- or diethanolamides of acids derived from copra, fromlauric acid or from oleic acid, in concentrations between 0 and 10%.

Representative fatty alcohols include, in particular, oleyl alcohol,tetradecyl alcohol, cetyl alcohol, stearyl alcohol and isostearylalcohol,in amounts between 0 and 10%.

The creams can also be formulated with natural or synthetic alcoholshaving12-18 carbon atoms in admixture with emulsifiers. Representativefatty alcohols include, in particular, the alcohol derived from thefatty acids of copra, tetradecyl alcohol, cetyl alcohol, stearyl alcoholand hydroxy stearyl alcohol, in concentrations between 5 and 25%.

Representative emulsifiers include the following:

non-ionic surfactants, such as oxyethylenated or polyglycerolated fattyalcohols, such as for example, oleyl alcohol polyoxyethylenated with 10moles of ethylene oxide, cetyl alcohol oxyethylenated with 6 to 10 molesof ethylene oxide, cetyl stearyl alcohol oxyethylenated with 10 moles ofethylene oxide, stearyl alcohol oxyethylenated with 10-15 or 20 moles ofethylene oxide, oleyl alcohol polyglycerolated with 4 moles of glyceroland synthetic fatty alcohols having 9-15 carbon atoms polyoxyethylenatedwith 5 or 10 moles of ethylene oxide. These non-ionics are present inamount of 5 to 25 weight percent;

anionic surfactants, such as alkyl sulfates oxyethylenated or not,including sodium lauryl sulfate, ammonium lauryl sulfate, sodium cetylstearyl sulfate, triethanolamine cetyl stearyl sulfate, monoethanolaminelauryl sulfate, sodium lauryl ether sulfate oxyethylenated with, forexample, 2.2 moles of ethylene oxide and monoethanolamine lauryl ethersulfate oxyethylenated with, for example, 2.2 moles of ethylene oxide.These constituents are present in an amount between 3 and 15 weightpercent.

Representative fatty amides include oleic diethanolamide, copra mono- ordi-ethanolamide and stearic monoethanolamide. These amides are used inamounts between 0 and 10 weight percent.

When the compositions of the present invention constitute hair dyecreams, they can include, in addition to the crosslinkedpolyamino-polyamide, various components recited in the above definedcreams which impart a cream consistency to the composition. There isalso included an alkalizingagent and a hair dye.

The pH of these compositions is generally between 9 and 11, the pH beingregulated by the addition of an appropriate alkalizing agent in the dyesupport. For example ammonia, monoethanolamine, diethanolamine ortriethanolamine can be added to the dye support or vehicle.

The hair dyes are oxidation dyes to which can be added direct dyes suchas an azo, an anthraquinone, or a nitrobenzene dye, an indamine, anindoaniline, an indophenol or other oxidation dyes such as the leucoderivatives of these compounds.

When the compositions of the present invention constitute shampooformulations, they include, in addition to the crosslinkedpolyamino-polyamide polymer, at least one anionic, cationic, non-ionicor amphoteric detergent.

Representative anionic surfactants include the following compounds, aswellas their mixtures:

the alkaline salts, the magnesium salts, the ammonium salts, the aminesalts or the amino alcohol salts of the following compounds:

alkyl sulfates, alkyl ether sulfates wherein the alkyl has a C₁₂ to C₁₈linear chain, ethoxylated alkylamide sulfates and ether sulfates withlinear C₁₂ to C₁₈ chains, alkylaryl polyether sulfates and monoglyceridesulfates;

alkylsulfonates wherein the alkyl has a C₁₂ to C₁₈ linear chain,alkylamide sulfonates, alkylarylsulfonates and α-olefin sulfonateshaving C₁₂ to C₁₈ linear chains;

alkylsulfosuccinates, alkylethersulfosuccinates, andalkylamidesulfosuccinates wherein the alkyl moeity is a C₁₂ -C₁₈linearchain;

alkylsulfosuccinamates wherein the alkyl moiety is a C₁₂ to C₁₈ linearchain;

alkylsulfoacetates wherein the alkyl is a C₁₂ to C₁₈ chain;

alkyl phosphates and alkyletherphosphates wherein the alkyl is a C₁₂ toC₁₈ chain;

alkylsarcosinates, alkylpolypeptidates, alkylamidopolypeptidates,alkylisethionates and alkyl taurates wherein the alkyl is a C₁₂ to C₁₈chain; and

fatty acids such as oleic acid, ricinoleic acid, palmitic acid, stearicacid, the acids of copra oil, or of hydrogenated copra oil, carboxylicacids and carboxylic acids of polyglycol ethers of the formulaAlk--(OCH₂ --CH₂)_(n) --OCH₂ --CO₂ H wherein Alk is a C₁₂ to C₁₈ linearchain and n is a whole number from 5 to 15.

Representative cationic surfactants include, alone or in admixture, thefollowing materials:

salts of fatty amines, such as alkylamine acetates;

quaternary ammonium salts, such as alkyl dimethylbenzylammonium chlorideorbromide, alkyl trimethylammonium chloride or bromide, alkylmethylhydroxyethylammonium chloride or bromide,dimethyldistearylammonium chloride or bromide and methosulfates ofalkylamido ethyltrimethylammoniumchloride or bromide,

salts of alkylpyridinium, and

imidazoline derivatives.

Further, amine oxides having a cationic character such asalkyldimethylamine oxide or alkylaminoethyl dimethylamine oxide can alsobe used.

Representative non-ionic surfactants which can be used in admixture withthe previously defined anionics, include:

condensation products of a mono alcohol, an α-diol, an alkylphenol oranamide with glycidol. Such products include, for example, compounds ofthe formula R--CHOH--CH₂ --O--(CH₂ --CHOH--CH₂ --O)_(n) H, wherein Rrepresents an aliphatic, cycloaliphatic or arylaliphatic radical having7 to 21 carbon atoms and their mixtures, the aliphatic chains being ableto have ether, thioether and hydroxymethylene groups and1≦n≦10; andcompounds of the formula RO--C₂ H₃ O(CH₂ OH)]_(n) H wherein R representsalkyl, alkenyl or alkaryl having from 8 to 22 carbon atoms and nrepresents a number between 1 and 10;

alcohols, alkylphenols or polyglycerolated or polyethoxylated fattyacids having a linear fatty C₈ to C₁₈ chain carrying most often from 2to15 moles of ethylene oxide, for example lauryl alcoholpolyoxyethylenated with 12 moles of ethylene oxide;

copolymers of the oxides of ethylene and propylene;

the condensates of ethylene oxide and propylene oxide on fatty alcohols;

polyethoxylated fatty amides;

polyethoxylated fatty amines;

ethanolamides;

esters of fatty acids of glycol;

esters of fatty acids of sorbitol; and

esters of fatty acids of sucrose.

Representative amphoteric surfactants which can be used includeprincipally:

alkylamino mono- and di-propionates;

betaines, such as N-alkyl betaines, N-alkylsulfobetaines andN-alkylamidobetaines; and

cycloimidinium (alkylimidazolines).

All these detergents, as well as numerous others not mentioned here butnonetheless useful in the shampoos according to the present invention,arewell known and are described in the literature.

The compositions of the present invention in the form of shampoos canalso contain various adjuvants such as for example perfumes, dyes,preservatives, thickening agents, foam stabilizers, softening agents andcosmetic resins.

Representative foam stabilizers include fatty amides and particularlycopramono- or di-ethanolamides, and lauric mono- or di-ethanolamides.

In these shampoo formulations, the detergent concentration is generallybetween 3 and 50 weight percent relative to the total weight of thecomposition, and preferably from 3 to 20 weight percent, and the pH isgenerally between 3 and 9.

When the compositions of the present invention constitute lotions, theycanbe styling lotions, forming lotions (called "brushing lotions"),non-rinse reinforcing hair setting lotions, rinsing lotions (called"rinses") and the like.

By a "brushing lotion" is meant a lotion which is applied aftershampooing and which improves the styling of the hair which is effectedon damp or moist hair with the aid of a brush, during the drying of thehair with theaid of a hand dryer.

By a non-rinse reinforcing hair setting lotion is meant a lotion whichis applied after shampooing and before setting the hair and which lotionis not rinsed from the hair. This lotion facilitates setting the hairand improves the durability of the hair set.

These lotions include, in an aqueous, alcoholic or hydroalcoholicsolution at least one crosslinked polyamino-polyamide such as definedabove. They can also contain:

film forming polymers such as polyvinylpyrrolidone, copolymers ofvinylpyrrolidone and vinyl acetate, copolymers resulting from thepolymerization of vinyl acetate and vinyl alkl ether.

Representative preferred resins, include polyvinylpyrrolidone having amolecular weight of 10,000 to 70,000; copolymers of vinylpyrrolidone(VP) and vinyl acetate (VA) having a molecular weight of 30,000 to200,000, theVP:VA ratio being between 30:70 and 70:30; and terpolymersof methyl methacrylate (15-25%)-stearyl methacrylate (18-28%) anddimethylaminoethylmethacrylate (52-62%) quaternized or not by methylsulfate.

The composition can also contain: quaternary polyvinylpyrrolidonecopolymers, such as for example a polymer having a molecular weight intheorder of 1,000,000 and sold under the mark "Gafquat 755", and apolymer having a molecular weight in the order of 100,000 sold under themark "Gafquat 734"; graft cationic copolymers resulting from thecopolymerization of 3 to 95 weight percent N-vinylpyrrolidone, from 3 to95 weight percent dimethylaminoethyl methacrylate and 2 to 50 weightpercent polyethyleneglycol such as those described in French Pat. No. 7615 948; corresponding essentially to U.S. patent application Ser. No.690.783 filed May 27, 1976, now U.S. Pat. No. 4,047,888; cationicpolymersresulting from the condensation of piperazine or its derivatives(1) on bi-functional compounds such as alkyl or alkyl aryl dihalides,bisepoxides, epihalohydrins, and bis-unsaturated derivatives, (2) on aprimary amine whose two hydrogen atoms can be substituted and whichfunction as a bi-functional compound; (3) both on an epihalohydrin andon a hydroxylated amine such as diglycolamine,2-amino-2-methyl-1,3-propanediol or on an amino acid such as glycocoll,quaternized celluloses such as "JR 400".

In these lotions, the polymer concentration is generally between 0.1 and5 weight percent and preferably between 0.1 and 3 weight percent and thepH is generally between 3 and 9.

By rinse lotion is meant a lotion that is applied to the hair before orafter a hair dyeing or bleaching operation, before or after ashampooing, or between successive shampooings, before or after apermanent wave operation, so as to obtain a conditioning effect of thehair. Such a lotion is rinsed from the hair after a short contact timetherewith.

These cosmetic rinse compositions of the present invention can be in theform of aqueous or hydroalcoholic solutions containing or not surfaceactive agents, or emulsions, or gels. Further these rinse compositionscanbe pressurized in aerosol containers. The surfactants used in theserinse lotions are principally non-ionic or cationic surfactants such asthose described in the shampoo compositions above and more particularly:

condensation products of a mono alcohol, an α-diol, an alkylphenol oranamide with glycidol; for example, compounds of the formula R--CHOH--CH₂--O--(CH₂ --CHOH--CH₂ --O)_(n) H wherein R represents an aliphatic,cycloaliphatic or arylaliphatic radical having 7 to 21 carbon atoms andtheir mixtures, the aliphatic chains being able to have ether, thioetherand hydroxymethylene groups and 1≦n≦10; and compounds of the formulaRO--[C₂ H₃ O(CH₂ OH)]_(n) H wherein R represents alkyl, alkenyl oralkylaryl having 8 to 22 carbon atoms and n is 1 to 10;

alcohols, alkylphenols or fatty acids, polyethoxylated orpolyglycerolated,having a C₈ to C₁₈ linear fatty chain, and having mostoften from2 to 15 moles of ethylene oxide.

The concentration of the surfactant in the rinse lotion can vary from 0to 7 weight percent.

An anionic or amphoteric surfactant can also be included in these rinselotions.

When the compositions are provided in the form of emulsions, they can benon-ionic or anionic. The non-ionic emulsions are constituted by amixtureof oils, and/or waxes, fatty alcohols and polyethoxylated fattyalcohols, such as stearyl or cetyl stearyl alcohols polyoxyethylenatedfor example with 10 moles of ethylene oxide. Cationic surfactants suchas for example those defined above can also be employed.

The anionic emulsions are constituted from soaps. Representativeemulsions include the selfemulsifiable emulsion constituted by glycerinestearate, sold under the name IMWITOR 960K and emulsions constituted bya combination of glycerine monostearate with esters of citric acid orwith fatty alcohols and lipopeptides or with alkaline stearates, soldrespectively under the names LAMEFORM ZEM, PLM and NSM.

When the compositions are provided in the form of gels they containthickening agents in the presence or not of solvents.

Representative thickening agents include sodium alginate or gum arabicor cellulose derivatives such as methyl cellulose, hydroxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,carboxymethyl cellulose or carboxylic polymers such as the "Carbopols".Thickening of the lotions can also be obtained by using polyethyleneglycols and stearates or distearates of polyethylene glycols, or byusing phosphoric esters and amines.

The concentration of the thickening agent can vary from 0.5 to 30 weightpercent and preferably from 0.5 to 15 weight percent.

The pH of these rinse lotions varies generally from 2 to 9.5.

When the compositions of the invention constitute restructuring lotions,they contain products which reinforce the keratin chain of the hair.

Such products include methylol derivatives such as those described inFrench Pat. Nos. 1,527,085 and 1,519,979 corresponding essentially toU.S.Pat. No. 3,773,056.

The following non-limiting examples are given to illustrate the presentinvention. Unless otherwise stated, all parts and percentages are byweight.

EXAMPLES OF PREPARATION EXAMPLE A--POLYCONDENSATION OF EQUIMOLAR AMOUNTSOF ADIPIC ACID AND DIETHYLENE TRIAMINE.

The resulting polymer is characterized by the following unit:

    --OC--(CH.sub.2).sub.4 --CONH--(CH.sub.2 --CH.sub.2 --NH.sub.2).sub.2 --

To 619 g (6 moles) of diethylene triamine, there are added, withagitation and under a nitrogen atmosphere and over a 15 minute period,876 g (6 moles) of adipic acid. The reaction mixture is then heated to145°-150° C., the temperature at which condensation of wateris observed.The reaction mixture is maintained at reflux for 45 minutes atwhich timethe water is removed by distillation, initially at ambient pressure for2 hours and then under reduced pressure (15 mm Hg) for 1 hour. Theheating temperature increases progressively up to 170° C.

The product thus obtained is poured out hot. After cooling, the productis in the form of a hard and brittle resin. It is transparent, has ayellow green color and is completely soluble in water.

EXAMPLE IA

Preparation of a quaternized crosslinking agent of the formula ##STR16##

To 236 g of a chloroform solution containing 57.2 g (0.289 mole) ofbis(epoxypropyl)piperazine, there are added, over a one hour period,36.4 g (0.289 mole) of dimethyl sulfate while maintaining the reactionmixture under agitation at 30° C.

The quaternized derivative is then precipitated from its solution in alarge excess of ether. After drying, there is recovered a very viscousoil, having an epoxide titer of 5.19 meq/g.

EXAMPLE IB

Crosslinking, with the crosslinking agent in Example IA, thepolyamino-polyamide polymer obtained by condensation of adipic acid ondiethylene triamine.

To 500 g of an aqueous solution containing 100 g (0.585 amineequivalent) of polyamino-polyamide prepared by condensation of equimolaramounts of adipic acid and diethylene triamine, according to Example A,there are added, at ambient temperature, 22 g (0.057 mole) ofquaternized crosslinking agent prepared in Example Ia. The temperatureof the reactionmedium is then raised to 90° C.

After 20 minutes, gelling of the solution is observed. There are thenrapidly added 698 g of water whereby a clear solution, yellow green incolor, having 10% active material is obtained. The viscosity of thissolution measured at 25° C. is 0.68 p at 87.93 sec.⁻¹.

EXAMPLE IIA

Preparation of a quaternized crosslinking agent of the formula ##STR17##

To 187.3 g of a chloroform solution containing 54.9 g (0.277 mole) ofbis(epoxypropyl)piperazine, there are added, over a 1 hour period, 70 g(0.555 mole) of dimethyl sulfate, while maintaining the reaction mediumunder agitation at 30° C.

The medium thickened during the course of the addition and solidifiesafterseveral hours at ambient temperature. The past is dissolved hot indimethylformamide. When cold, the solution gives up white crystalshaving a meltingpoint of 205° C., for which the epoxide index is 4.25meg/g.

EXAMPLE IIB

Crosslinking, with the crosslinking agent prepared in Example IIA, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene triamine is prepared.

To 476 g of an aqueous solution containing 95.2 g (0.557 amineequivalent) of the polyamino-polyamide prepared in Example A, there areadded, at ambient temperature, 20 g (0.0425 mole) of the crosslinkingagent preparedin Example IIA. The reaction mixture is maintained withagitation at 90° C. for 1 hour. Then the solution is adjusted to 10%active material by the addition of 656 g of water.

The solution is clear and has a yellow green color. Its viscosity,measuredat 25° C. is 0.27 p at 87.98 sec.⁻¹.

EXAMPLE IIIA

Preparation of a bis-unsaturated oligomer crosslinking agent obtainedfrom piperazine bis-acrylamide and piperazine in molar porportions of3/2 and having the formula: ##STR18##

To 380 g of an aqueous solution containing 194 g of bisacrylamide (1mole) there are added, over a one hour period, and between 10 and 15°C.,223 g of an aqueous solution containing 56.8 g (0.66 mole) ofpiperazine. The reaction medium is then left to stand for 24 hours atambient temperature. The solution is cloudy and thickens. It isclarified by heating and is then poured slowly into 5 liters of acetone.The crosslinking agent precipitates. After filtration and drying, awhite solid of which the dry extract is 80% is recovered.

EXAMPLE IIIB

Crosslinking, with the crosslinking agent prepared in Example IIIA, thepolyamino-polyamide polymer obtained by condensation of adipic acid ondiethylene triamine is prepared.

To 370 g of an aqueous solution containing 111 g (0.649 amineequivalent) of the polyamino-polyamide prepared according to Example A,there are added, at ambient temperature, 50 g of the crosslinking agentprepared in EXAMPLE IIIA. The temperature of the reaction medium is thenraised to 90° C. After 30 minutes the medium gels. The solution israpidly adjusted to 10% dry extract by the addition thereto of 1050 g ofwater.

A clear, yellow green solution is obtained. The viscosity of thissolution measured at 25° C. is equal to 58 centipoises.

EXAMPLE IVA

Bis-halohydrin oligomer crosslinking agent prepared from epichlorohydrinand piperazine in molar proportions of 5/4 and having the formula##STR19##where n=4.

To 541 g of an aqueous solution containing 69.4 g (0.806 mole) ofpiperazine, there are added, over a 1 hour period, without exceeding 20°C., 92.5 g (1 mole) of epichlorohydrin. The reaction mixture isagainmaintained for 1 hour with agitation at 20° C.; then at the sametemperature there are added 60 g (0.6 mole) of 40% NaOH over a 1hourperiod.

EXAMPLE IVB

Crosslinking, with the crosslinking agent prepared in Example IVA, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene triamine is prepared.

To 787.5 g of an aqueous solution containing 157.5 g (0.92 aminemilliequivalent) of the polyaminopolyamide prepared in Example A, thereare added, at ambient temperature, 268 g of an aqueous solutioncontaining54.9 g of the crosslinking agent prepared in Example IVa. Thetemperature of the reaction medium is maintained for 4 h 50 min at 90°C. At this point, the reaction medium gels. By rapid addition of 1100 ccof water there is obtained a clear solution having 9.85% activematerial. Theviscosity of this solution, measured at 25° C. is equal to73 centipoises.

EXAMPLE VA

Preparation of a quaternized crosslinking agent having the formula##STR20##wherein n=4.

To 330 g of an aqueous solution containing 67.7 g (0.752 amineequivalent) of the crosslinking agent prepared in Example IVA, there areadded, over a1 hour period and without exceeding 30° C., 47.4 g (0.376mole) of dimethylsulfate. The reaction medium is maintained withagitation for an additional 2 hours at this temperature.

EXAMPLE VB

Crosslinking, with a crosslinking agent prepared in Example Va, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene triamine is prepared.

To 327.7 g of an aqueous solution containing 65.5 g (0.383 amineequivalent) of the polyamino-polyamide prepared in Example A, there areadded, at ambient temperature, 155 g of an aqueous solution containing47.25 g of the crosslinking agent prepared in Example Va. After 4 hoursofheating at 85° C., the reaction mixture gels.

By rapid addition of 645 g of water, there is obtained a clear solutionhaving 10% active material. The viscosity of this solution measured at25° C. is 0.47 poise at 67.18 sec.⁻¹.

EXAMPLE VIA

Preparation of bis-azetidinium crosslinking agent of the formula##STR21##

To 50 g (0.212 mole) of 1,3-bis piperazine-2-propanol, (prepared by theaddition of epichlorohydrin to piperazine - as described in Example 15of French application No. 74 42279 of Nov. 28, 1972, or in Example 15 ofU.S.Pat. No. 3,917,817) dissolved in 100 g of absolute ethyl alcohol,there areadded at a temperature between 0 and 5° C., 43.5 g (0.47 mole)of epichlorohydrin. The reaction mixture is left to stand 24 hours at 0°C. The crosslinking agent is then precipitated from its solutionin alarge excess of ether. A white solid having a softening point ofabout120° C. is isolated.

EXAMPLE VIB

Crosslinking, with a crosslinking agent, prepared in Example VIa, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene triamine is prepared.

To 386 g of an aqueous solution containing 77.2 g (0.452 amineequivalent) of the polyamino-polyamide prepared in Example A, there areadded, at ambient temperature, 15.4 g (0.036 mole) of the crosslinkingagent prepared in Example VIa. After 2 hr. 30 min. of heating at 90° C.,the reaction medium gels. By rapid addition of 525 g of water, there isobtained a clear solution having 10% active material. The viscosity ofthis solution measured at 25° C. is 0.7 poise at 67.18 sec.⁻¹.

EXAMPLE VIIA

Preparation of bis-(chloracetyl)piperazine crosslinking agent of theformula: ##STR22##

This crosslinking agent is prepared by condensing 2 molecules ofchloracetyl chloride on a molecule of piperazine in the presence ofNaOH.

EXAMPLE VIIB

Crosslinking, with the crosslinking agent prepared in Example VIIa, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene triamine is prepared.

To 100 g of an aqueous solution containing 200 g (1.170 amineequivalents) of the polyamino-polyamide prepared in Example A, there areadded, at ambient temperature, 24 g (0.1 mole) ofbis-(chloracetyl)piperazine. The temperature of the reaction medium isthen raised to 90° C. After 30 minutes of heating the reaction mediumgels. Then 1216 g of water are rapidly added and heating is continued at80° C. for 1 hour. A clear solution is obtained having 10% activematerial. The viscosity of this solution measured at 25° C. is 0.29poise at 88.41 sec.⁻¹.

EXAMPLE VIIIA

Preparation of bis-(1,1-bromo undecanoyl)piperazine crosslinking agentof the formula ##STR23##

This crosslinking agent is prepared by the condensation of 2 moleculesof bromoundecanoyl bromide and one molecule of piperazine in thepresence of sodium hydroxide.

EXAMPLE VIIIB

Crosslinking, with the crosslinking agent prepared in Example VIIIa, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene triamine is prepared.

To 113.3 g of an aqueous solution containing 56.7 g (0.33 amineequivalent)of the polyamino-polyamide prepared in Example A, there areadded, at ambient temperature, 60 g of an isopropanol solutioncontaining 10 g (0.017 mole) of bis-(1,1-bromo undecanoyl) piperazine,prepared in ExampleVIIIa. The reaction medium is heated 2 hr. 30 min. atsolvent reflux. The isopropanol is then distilled, while adding wateruntil the attainment of a 10% aqueous solution of the resin (activematerial). The solution is slightly opalescent and its viscosity,measured at 25° C. is 0.052 poise at 87.93 sec.⁻¹.

EXAMPLE IXA

Preparation of an oligomer crosslinking agent of the formula##STR24##from epichlorohydrin and piperazine in molar proportions of4/3.

To 1149 g of an aqueous solution containing 172 g (12 moles) ofpiperazine there are added, over a 1 hour period, 246.7 g (2.66 moles)of epichlorohydrin while maintaining the reaction mixture with agitationat 20° C.

After an additional hour of agitation at 20° C., there are added, atthesame temperature and in the space of 1 hour, 133 g (1.33 mole) of 40%NaOH. A precipitation in the course of neutralization is observed. Thereare then added 638 g of water and the mixture is heated a few minutes at50° C. to obtain a clear solution.

EXAMPLE IXB

Crosslinking, with the crosslinking agent prepared in Example IXA, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene diamine.

To 2000 g of an aqueous solution containing 400 g (2.34 amineequivalents) of the polyamino-polyamide prepared according to Example A,there are added 584 g of an aqueous solution containing 99.8 g of thecrosslinking agent prepared in Example IXA. The reaction medium is thenmaintained withagitation at 90° C. for 5 hours. There are then added2,414 g of water to obtain a clear solution having 10% active material.The viscosityof this solution measured at 25° C. is 0.22 poise.

EXAMPLE XA

Preparation of an oligomer crosslinking agent of the formula:##STR25##from epichlorohydrin and piperazine in molar proportions of3/2.

To 1,221 g of an aqueous solution containing 172 g (2 moles) ofpiperazine there are added, over a 1 hour period and at 20° C., 277.5 g(3 moles) of epichlorohydrin while maintaining the reaction mixtureunder agitation and at 20° C. After an additional hour of agitationthereare added, at a temperature of 20° C., 100 g (1 mole) of a 40%aqueous solution of NaOH.

On addition of 727.5 g of water and after a few minutes of heating, aclearsolution of the said crosslinking agent is obtained.

EXAMPLE XB

Crosslinking, with the crosslinking agent prepared in Example XA, thepolyamino-polyamide polymer obtained by the condensation of adipic acidondiethylene triamine is prepared.

To 2,000 g of an aqueous solution containing 400 g (2.34 amineequivalents)of the polyamino-polyamide prepared in accordance withExample A, there areadded 472 g of an aqueous solution containing 83.3 gof the crosslinking agent prepared in Example XA.

The reaction medium is maintained with agitation at 90° C. and after4hours of heating, the solution gels.

The solution is rapidly adjusted to 10% active material by the additionof 2,326 g of water.

A clear solution is obtained. The viscosity of this solution measured at25° C. is 0.64 poise at 88.4 sec.⁻¹.

EXAMPLES OF USE EXAMPLE 1A

A rinse composition is prepared by admixing the following components:

    ______________________________________                                        Compound of Example VIb 0.5 g  active                                                                        material                                        ##STR26##              0.5 g  active material                                RCHOHCH.sub.2O(CH.sub.2CHOHCH.sub.2O).sub.nH                                  wherein R = C.sub.9 -C.sub.10 alkyl                                           and n has a statistical                                                       average value of 3.5    0.7g                                                  Phosphoric acid ester of                                                      ethoxylated oleyl                                                             alcohol sold under the                                                        name "DIVALIN SO"       0.4g                                                  Water, sufficient for   100 cc                                                ______________________________________                                    

The pH of this solution is 7-8. This rinse composition is applied topreviously washed hair. The combing of the thus treated hair isexcellent.The dry hair is particularly full, shiny and easy to style.

EXAMPLE IB

A rinse composition is prepared by admixing the following components:

    ______________________________________                                        Polymer obtained by the                                                       condensation of equimolar                                                     amounts of adipic acid and                                                    diethylene triamine and                                                       crosslinked with 0.11 mole                                                    of epichlorohydrin per                                                        amine group (according to                                                     Example 1a of S.N. 762,804)                                                                         0.5 g   active                                                                        material                                        Compound of Example VIIIb                                                                           0.5 g   active                                                                        material                                        R CHOHCH.sub.2O(CH.sub.2CHOHCH.sub.2O).sub.nH                                 wherein R = C.sub.9 -C.sub.10 alkyl and                                       n has a statistical average                                                   value of 3.5          0.7 g                                                   Phosphoric acid ester of                                                      ethoxylated oleyl alcohol                                                     sold under the mark                                                           "DIVALIN SO"          0.4 g                                                   Water, sufficient for 100 cc                                                  ______________________________________                                    

The pH of this solution is 7-8. This rinse composition is applied topreviously washed hair. The combing of the thus treated hair isexcellent.The dry hair is particularly full, shiny and easy to style.

EXAMPLE 1c

An emulsion having the following composition is prepared:

    ______________________________________                                        Petrolatum oil            15 g                                                Cetyl-stearyl alcohol, partially                                              sulfated, sold under the                                                      mark "Cire de lanette"    2.5 g                                               Cetyl stearyl alcohol poly-                                                   oxyethylenated with 10                                                        moles of ethylene oxide,                                                      sold under the name                                                           "SIMULSOL 1951 RD"        2.5 g                                               Compound of Example VIIb  0.7 g                                               Water, sufficient for     100 g                                               ______________________________________                                    

The pH of this solution is 9.5. Its application, followed by rinsing offthis "rinse" in the form of an emulsion on the hair, facilitates itsuntangling; imparts to it softness; and gives good liveliness to thehair style.

EXAMPLE 1d

An emulsion having the following composition is prepared:

    ______________________________________                                        Petrolatum oil            15 g                                                Cetyl stearyl alcohol, partially                                              sulfated, sold under the                                                      mark "Cire de lanette"    2.5 g                                               Cetyl stearyl alcohol poly-                                                   oxyethylated with 10 moles                                                    of ethylene oxide, sold                                                       under the name                                                                "SIMULSOL 1951 RD"        2.5 g                                               Compound of Example IIIb  0.5 g                                               Water, sufficient for     100 g                                               ______________________________________                                    

The pH of this solution is 9. This "rinse" is applied to the hair, andleftin contact therewith for a few minutes. It is then rinsed off. Theuntangling of the hair is facilitated; the hair has a firmer touch; andthe liveliness of the hair style is improved.

EXAMPLE 2a

A hair setting lotion is prepared by admixing the following components:

    ______________________________________                                         ##STR27##              0.5 g   active material                               Compound of Example VIb 0.5 g   active                                                                        material                                      Quaternary polyvinylpyrrolidone                                               copolymer having a molecular                                                  weight of about 100,000,                                                      sold under the name                                                           "GAFQUAT 734"           0.4 g   active                                                                        material                                      Perfume                 0.2 g                                                 Dyes                    0.05 g                                                Water, sufficient for   100 cc                                                ______________________________________                                    

The pH of this lotion is 7.3. When applied to dyed hair, this hairsetting lotion facilitates the combing of wet hair. The dry hair is softand easy to style. This effect of softness lasts after severalshampooings.

EXAMPLE 2b

The following hair setting composition is prepared:

    ______________________________________                                        Compound of Example Ib                                                                              0.5 g   active                                                                        material                                        Quaternary polyvinylpyrrolidone                                               copolymer having a molecular                                                  weight of about 100,000, sold                                                 under the name "GAFQUAT 734"                                                                        0.4 g   active                                                                        material                                        Perfume               0.1 g                                                   Dyes                  0.01 g                                                  Water, sufficient for 100 cc                                                  ______________________________________                                    

The pH of this composition is 7.3. When applied to dyed hair, this hairsetting lotion facilitates the combing of wet hair. The dry hair is softand easy to style. This effect of softness lasts after severalshapooings.

EXAMPLE 2c

The following hair setting lotion is prepared:

    ______________________________________                                        Compound of Example IIb                                                                             0.6 g   active                                                                        material                                        Quaternary polyvinyl-                                                         pyrrolidone copolymer having                                                  a molecular weight of about                                                   100,000 and sold under the                                                    name "Gafquat 734"    0.5 g                                                   Quaternized cellulose sold                                                    under the name                                                                "JR 400"              0.3 g                                                   Ethyl alcohol, sufficient for                                                                       15°                                              Perfume               0.1 g                                                   Water, sufficient for 100 cc                                                  pH, adjusted to 8                                                             ______________________________________                                    

When applied to washed hair, this hair setting lotion facilitatescombing. After drying and setting the hair, the hair is soft, shiny andis easy to style. This effect lasts after several shampooings.

EXAMPLE 2d

The following hair setting lotion is prepared:

    ______________________________________                                        Compound of Example IVb                                                                             0.3 g   active                                                                        material                                        Quaternary polyvinylpyrrolidone                                               copolymer having a molecular                                                  weight of about 100,000 and                                                   sold under the name                                                           "Gafquat 734"         0.5 g                                                   Quaternary cellulose, sold                                                    under the name "JR 400"                                                                             0.3 g                                                   Ethyl alcohol, sufficient for                                                                       15°                                              Perfume               0.1 g                                                   Water, sufficient for 100 cc                                                  pH, adjusted to 8                                                             ______________________________________                                    

When applied to washed hair, this setting lotion facilitates combing.Afterdrying and setting, the hair is soft, shiny and easy to style. Thiseffect last after several shampooings.

EXAMPLE 3a

The following "brushing lotion" is prepared:

    ______________________________________                                        Compound of Example Vb 0.6 g  active                                                                        material                                        Ethanol, sufficient for                                                                              10°                                             Dyes                   0.1 g                                                  Perfume                0.1 g                                                  Water, sufficient for  100 g                                                  The pH of this solution is adjusted to 7.                                     ______________________________________                                    

EXAMPLE 3b

The following "brushing lotion" is prepared:

    ______________________________________                                        Compound of Example IIIb                                                                             0.4 g   active                                                                        material                                       Ethanol, sufficient for                                                                              10°                                             Dyes                   0.1 g                                                  Perfume                0.1 g                                                  Water, sufficient for  100 cc                                                 The pH of this solution is adjusted to 8.                                     ______________________________________                                    

EXAMPLE 3c

The following "brushing lotion" is prepared:

    ______________________________________                                        Compound of Example VIIIb                                                                            0.5 g   active                                                                        material                                       Ethanol, sufficient for                                                                              20°                                             Dyes                   0.2 g                                                  Perfume                0.1 g                                                  Water, sufficient for  100 cc                                                 The pH of this solution is adjusted to 6.                                     ______________________________________                                    

EXAMPLE 3d

The following "brushing lotion" is prepared:

    ______________________________________                                        Compound of Example Ib 0.5 g   active                                                                        material                                       Dyes                   0.1 g                                                  Perfume                0.1 g                                                  Water, sufficient for  100 cc                                                 The pH of this solution is adjusted to 5.                                     ______________________________________                                    

EXAMPLE 3e

The following "brushing lotion" is prepared:

    ______________________________________                                        Compound of Example IIb                                                                              0.8 g   active                                                                        material                                       Ethanol, sufficient for                                                                              40°                                             Dyes                   0.05 g                                                 Perfume                0.1 g                                                  Water, sufficient for  100 cc                                                 The pH of this solution is adjusted to 7.                                     ______________________________________                                    

EXAMPLE 3f

The following "brushing lotion" is prepared:

    ______________________________________                                        Compound of Example VIIb                                                                             0.6 g   active                                                                        material                                       Dyes                   0.05 g                                                 Perfume                0.15 g                                                 Water, sufficient for  100 cc                                                 The pH of this solution is adjusted to 6.                                     ______________________________________                                    

The "brushing lotions" of Examples 3a-3f are applied to wet or dry hairafter shampooing. The hair is styled using a brush, all while drying thehair with the aid of a hand dryer. Very good passage of the brushthrough the hair is noted as is a prolonged holding of the style. Thehair thus treated is shiny and soft.

EXAMPLE 4a

The following shampoo composition is prepared:

    ______________________________________                                        Triethanolamine C.sub.12 -C.sub.14                                            alkyl sulfate                5 g                                              RCHOHCH.sub.2O(CH.sub.2CHOHCH.sub.2O).sub.nH                                  wherein R is C.sub.9 to C.sub.12 alkyl                                        and n has a statistical                                                       average value of 3.5         5 g                                              Lauric diethanolamide        3 g                                              Compound of Example VIb      1 g                                              Perfume                      0.1 g                                            Dyes                         0.01 g                                           Water, sufficient for        100 g                                            pH adjusted to 8 with triethanolamine.                                        ______________________________________                                    

This shampoo composition is provided in the form of a clear liquid. Itfacilitates combing wet hair and it imparts control and body to thehair.

EXAMPLE 4b

The following shampoo compositions is prepared:

    ______________________________________                                        RCHOH CH.sub.2O(CH.sub.2CHOHCH.sub.2O).sub.nH                                 wherein R is C.sub.9 to C.sub.12 alkyl                                        and n has a statistical                                                       average value of 3.5  10 g                                                    Copra diethanolamide  3 g                                                     Compound of Example IIIb                                                                            1 g     active                                                                        material                                        Water, sufficient for 100 g                                                   The pH of this composition initially was 8.7 and                              it was then adjusted to 6 using lactic acid.                                  ______________________________________                                    

When applied to natural hair, this shampoo composition, provided in theform of a clear liquid, facilitates combing wet hair. The dry hair isfulland lively.

EXAMPLE 4c

The following shampoo composition is prepared:

    ______________________________________                                        Ammonium lauryl sulfate 25 g                                                  Diethanolamide of the fatty                                                   acids of copra          2 g                                                   Compound of Example VIIIb                                                                             1 g    active                                                                        material                                       Water, sufficient for   100 g                                                 Initial pH of 8.1 adjusted to 7.7                                             with lactic acid.                                                             ______________________________________                                    

When applied to dyed, permanent waved hair, this slightly opalescentclear shampoo composition produces convenient untangling of wet hair.After drying the hair is full and lively.

EXAMPLE 4d

The following shampoo composition is prepared:

    ______________________________________                                        Lauryl alcohol poly-                                                          oxyethylenated with 12                                                        moles of ethylene oxide 5 g                                                   C.sub.12 -C.sub.18 alkyl dimethyl                                             carboxymethyl ammonium                                                        hydroxide, sold under the                                                     name "DEHYTON AB 30"    10 g                                                  Lauric diethanolamide   3 g                                                   Compound of Example Ib  0.8 g  active                                                                        material                                       Water, sufficient for   100 g                                                 The initial pH of 7.8 was adjusted to 6                                       with lactic acid.                                                             ______________________________________                                    

When applied to dyed hair, this shampoo composition, provided in theform of a slightly opalescent clear liquid, facilitates the combing ofwet hairand makes it softer. The dry hair is lively, full andcontrolled.

EXAMPLE 4e

The following shampoo composition is prepared:

    ______________________________________                                        Triethanolamine C.sub.12 -C.sub.14                                            alkyl sulfate       12.5 g                                                    Lauric diethanolamide                                                                             2 g                                                       Compound of Example IIb                                                                           0.7      active                                                                        material                                         Water, sufficient for                                                                             100 g                                                     pH = 7.4                                                                      ______________________________________                                    

When applied to natural hair, this clear liquid shampoo compositionprovides good untangling of wet hair. The dry hair is full, lively andcontrolled.

EXAMPLE 4f

The following shampoo composition is prepared:

    ______________________________________                                        C.sub.12 -C.sub.14 alcohol ethoxylated                                        with 10 moles of ethylene                                                     oxide and carboxymethylated,                                                  sold under the mark                                                           "AKYPO RLM 100"       3.5 g                                                   Lauryl alcohol polyethoxylated                                                with 12 moles of                                                              ethylene oxide        10 g                                                    Compound of Example IIB                                                                             0.6 g   active                                                                        material                                        Homopolymer of dimethyl diallyl                                               ammonium chloride, M.W. =                                                     about 100,000, sold under                                                     the mark "MERQUAT 100"                                                                              0.4 g   active                                                                        material                                        Water, sufficient for 100 g                                                   pH = 7.4                                                                      ______________________________________                                    

When applied to dyed hair, this liquid shampoo composition improves theuntangling of wet hair. The dry hair is controlled and shiny.

EXAMPLE 4g

A shampoo composition having the same formulation as that in Example 4fis prepared except that the 0.6 g of the compound of Example IIb isreplaced by 0.5 g of the compound of Example VIIIb.

The properties of this shampoo composition are similar to those of theshampoo composition of Example 4f.

EXAMPLE 4h

The following shampoo composition is prepared:

    ______________________________________                                        C.sub.12 -C.sub.14 alcohol ethoxylated                                        with 10 moles of ethylene                                                     oxide and carboxymethylated,                                                  sold under the mark                                                           "AKYPO RLM 100"       3.5 g                                                   Lauryl alcohol polyethoxylated                                                with 12 moles of ethylene oxide                                                                     10 g                                                    Compound of Example Ib                                                                              0.6 g   active                                                                        material                                        Homopolymer of dimethyl diallyl                                               ammonium chloride, M. W. =                                                    about 100,000, sold under the                                                 mark "MERQUAT 100"    0.4 g   active                                                                        material                                        Perfume               0.15 g                                                  Dyes                  0.02 g                                                  Water, sufficient for 100 g                                                   pH adjusted to 7                                                              ______________________________________                                    

When applied to dyed hair, this shampoo composition provides gooduntangling of wet hair and imparts to dry hair liveliness and fullness.

EXAMPLE 4i

The following shampoo composition is prepared:

    ______________________________________                                        Hydroxy propyl methyl                                                         cellulose            0.2 g                                                    Diethanolamide of the                                                         fatty acids of copra 3 g                                                      Triethanolamine C.sub.12 -C.sub.14                                            alkyl sulfate        10 g                                                     Compound of Example VIIb                                                                           0.8 g   active                                                                        material                                         Perfume              0.15 g                                                   Dyes                 0.01 g                                                   Water, sufficient for                                                                              100 g                                                    pH, adjusted to 7.8                                                           ______________________________________                                    

When applied to natural permanent waved hair, this shampoo compositionprovides good untangling of wet hair and imparts to dry hair livelinessand fullness.

EXAMPLE 4j

The following shampoo composition is prepared:

    ______________________________________                                        Lauryl alcohol polyethoxylated                                                with 12 moles of                                                              ethylene oxide        7 g                                                     RCHOHCH.sub.2O(CH.sub.2CHOHCH.sub.2O).sub.nH                                  wherein R = C.sub.9 to C.sub.12 alkyl                                         and n has a statistical                                                       average value of 3.5  7 g                                                     Diethanolamide of copra                                                       fatty acids           2 g                                                     Compound of Example IVb                                                                             0.8 g   active                                                                        material                                        Perfume               0.1 g                                                   Dyes                  0.01 g                                                  Water, sufficient for 100 g                                                   pH, adjusted to 7.2                                                           ______________________________________                                    

When applied to dyed hair, this shampoo composition provides gooduntangling of wet hair and imparts to dry hair liveliness and fullness.

EXAMPLE 4k

The following shampoo composition is prepared:

    __________________________________________________________________________    RCHOHCH.sub.2O(CH.sub.2CHOHCH.sub.2OH).sub.n                                  wherein R = C.sub.9 to C.sub.12 alkyl                                         and n has a statistical                                                       average value of 3.5        10 g                                              Diethanolamide of copra                                                       fatty acids                 3 g                                               Compound of Example IIb     0.5 g                                                                             active                                                                        material                                       ##STR28##                  0.2 g                                                                             active material                               Water, sufficient for       100 g                                             pH, initially 8.6; adjusted to                                                6 with lactic acid                                                            __________________________________________________________________________

When applied to natural hair, this shampoo composition in the form of aclear liquid, facilitates untangling of wet hair. Dry hair, thustreated, is controlled and shiny.

EXAMPLE 41

The following shampoo composition is prepared:

    __________________________________________________________________________    RCHOHCH.sub.2O(CH.sub.2CHOHCH.sub.2OH).sub.n                                  wherein R = C.sub.9 to C.sub.12 alkyl                                         and n has a statistical                                                       average value of 3.5        10 g                                              Triethanolamine C.sub.12 -C.sub.14                                            alkyl sulfate               2 g                                               Diethanolamide of copra                                                       fatty acids                 3 g                                               Compound of Example Ib      0.5 g                                                                             active                                                                        material                                       ##STR29##                  0.1 g                                                                             active material                               Water, sufficient for       100 g                                             pH, initially - 7.9; adjusted                                                 to 6 with lactic acid                                                         __________________________________________________________________________

When applied to dyed hair, this shampoo composition in the form of aslightly opalescent liquid facilitates the untangling of wet hair andimparts softness thereto. Dry hair, thus treated, is lively and full.

EXAMPLE 4m

The following shampoo composition is prepared:

    ______________________________________                                        C.sub.12 -C.sub.14 alcohol ethoxylated                                        with 10 moles of ethylene                                                     oxide and carboxymethylated,                                                  sold under the mark                                                           "AKYPO RLM 100"         3 g                                                   Lauryl alcohol polyethoxylated                                                with 12 moles of                                                              ethylene oxide          7 g                                                   Lauric diethanolamide   3 g                                                   Compound of Example IIIb                                                                              0.6 g   active                                                                        material                                       ##STR30##              0.3 g   active material                               Water, sufficient for   100 g                                                 pH, initially - 4.5; adjusted to                                              7.2 with triethanolamine                                                      ______________________________________                                    

When applied to dyed hair, this shampoo composition in the form of aclear liquid, facilitates the untangling of wet hair. Dry hair, thustreated is shiny.

EXAMPLE 4n

The following shampoo composition is prepared:

    __________________________________________________________________________    RCHOHCH.sub.2O(CH.sub.2CHOHCH.sub.2OH).sub.n                                  wherein R = C.sub.9 to C.sub.12                                               alkyl and n has a statistical                                                 average value of 3.5        10 g                                              Diethanolamide of copra                                                       fatty acids                 2 g                                               Compound of Example Ib      0.7 g                                                                             active                                                                        material                                       ##STR31##                  0.3 g                                             Water, sufficient for       100 g                                             pH = 7                                                                        __________________________________________________________________________

When applied to natural, permanent waved hair, this shampoo compositionin the form of a clear liquid, facilitates the untangling of wet hairand imparts softness thereto. Dry hair, thus treated, is lively, fulland easyto control.

EXAMPLE 4o

The following shampoo composition is prepared:

    ______________________________________                                        Triethanolamine C.sub.12 -C.sub.14                                            alkyl sulfate            10 g                                                 Lauric diethanolamide    2 g                                                  Hydroxypropylmethyl cellulose                                                                          0.2 g                                                Compound of Example Vb   0.8 g                                                Perfume                  0.1 g                                                Dyes                     0.01 g                                               Water, sufficient for    100 g                                                pH, adjusted to 8 with                                                        triethanolamine                                                               ______________________________________                                    

This clear liquid shampoo composition improves the untangling of wethair. It imparts to dry hair thus treated good control.

EXAMPLE 4p

The following shampoo composition is prepared:

    ______________________________________                                        Triethanolamine C.sub.12 -C.sub.14                                            alkyl sulfate            15 g                                                 Hydroxypropylmethyl cellulose                                                                          0.2 g                                                Lauric diethanolamide    3 g                                                  Compound of Example IXb  1 g                                                  Perfume                  0.2 g                                                Dyes                     0.01 g                                               Water, sufficient for    100 g                                                pH = 7.7                                                                      ______________________________________                                    

EXAMPLE 4q

The following shampoo composition is prepared:

    ______________________________________                                        Triethanolamine C.sub.12 -C.sub.14                                            alkyl sulfate            10 g                                                 Hydroxypropylmethyl cellulose                                                                          0.3 g                                                Compound of Example Xb   1 g                                                  Perfume                  0.1 g                                                Dyes                     0.015 g                                              Water, sufficient for    100 g                                                pH = 7.7                                                                      ______________________________________                                    

EXAMPLE 5a

The following "after-shampoo" care cream is prepared:

    ______________________________________                                        Cetyl alcohol            20 g                                                 Cetyl alcohol oxyethylenated                                                  with 10 moles of ethylene                                                     oxide, sold under the                                                         mark "BR1J 50"           12 g                                                  ##STR32##               1.5 g  active material                               Compound of Example VIIb 0.5 g  active                                                                        material                                      Phosphoric acid ester of                                                      ethoxylated oleyl alcohol,                                                    sold under the mark                                                           "DIVALIN SO"             1 g                                                  Water, sufficient for    100 g                                                ______________________________________                                    

EXAMPLE 5b

The following "after-shampoo" care cream is prepared:

    ______________________________________                                        Cetyl alcohol         22 g                                                    Cetyl alcohol oxyethylenated                                                  with 10 moles of ethylene                                                     oxide, sold under the mark                                                    "BR1J 56"             10 g                                                    Compound of Example IVb                                                                             0.5 g  active                                                                        material                                         Phosphoric acid ester of                                                      ethoxylated oleyl alcohol,                                                    sold under the mark                                                           "DIVALIN SO"          1.2 g                                                   Water, sufficient for 100 g                                                   ______________________________________                                    

The care creams of Examples 5a and 5b are applied to clean, moist ordried hair, in an amount sufficient to impregnate and cover the hair(about 60 to 80 g). The cream is permitted to remain in contact with thehair for 30-40 minutes at which time it is then rinsed off. The wet hairis very soft and easy to comb. The hair is then set and dried under ahood. The dry hair combs easily and has a silky touch; is shiny andlively; has bodyand is full.

EXAMPLE 5c

The following "before shampoo" care cream is prepared:

    ______________________________________                                        Stearic acid             12 g                                                 Cetyl-stearyl alcohol                                                         oxyethylenated with 10                                                        moles of ethylene oxide  4 g                                                  Monoethanolamine         2 g                                                  Glycerine                4 g                                                   ##STR33##               1.2 g  active material                               Compound of Example VIIIb                                                                              0.5 g  active                                                                        material                                      Perfume and dyes                                                              Water, sufficient for    100 g                                                pH, adjusted to 7                                                             ______________________________________                                    

EXAMPLE 5d

The following "before shampoo" care cream is prepared:

    ______________________________________                                        Stearic acid          12 g                                                    Cetyl-stearyl alcohol                                                         oxyethylenated with 10                                                        moles of ethylene oxide                                                                             6 g                                                     Monoethanolamine      3 g                                                     Glycerine             3 g                                                     Compound of Example IIIb                                                                            0.8 g  active                                                                        material                                         Perfume - Dyes                                                                Water, sufficient for 100 g                                                   pH, adjusted to 7                                                             ______________________________________                                    

The care creams of Example 5c and 5d are applied to soiled, wet hair ata rate of 60 grams. The hair is impregnated therewith by rubbing and thecream is permitted to remain in contact therewith for 30 minutes. Thehairis then shampooed. The wet hair is very soft and easy to untangle.After setting and drying, the hair has a particularly soft feel; it isshiny, lively and has body. This effect lasts after several shampooings.

EXAMPLE 6a

The following hair structuring lotion without rinsing is prepared:

    ______________________________________                                        Dimethylol ethylene thiourea                                                  of the formula                                                                 ##STR34##          0.5 g                                                     Quaternary polyvinylpyrrolidone                                               copolymer, M.W. = about                                                       1,000,000, sold under the                                                     mark "GAFQUAT 755"  0.5 g                                                     Compound of Example Ib                                                                            0.4 g      active                                                                        material                                       Vinylpyrrolidone-vinyl acetate                                                copolymer, VP/VA = 70:30                                                                          0.8 g                                                     Phosphoric acid, sufficient for                                                                   pH = 3                                                    Water, sufficient for                                                                             100 cc                                                    ______________________________________                                    

This lotion is applied to washed and dried hair after a shampoo andbefore setting. In the wet state the hair untangles easily and has asilky touch.After setting and drying, the hair is shiny and lively.

EXAMPLE 6b

This example is similar to Example 6a except that the compound ofExample Ib is replaced by an equal amount of the compound of ExampleIVb.

EXAMPLE 7a

The following non-rinse lotion for use before a permanent is prepared:

    ______________________________________                                        Trimethyl cetylammonium bromide                                                                     0.1 g                                                   Compound of Example IVb                                                                             1.5 g                                                   Perfume               0.1 g                                                   Dyes                  0.1 g                                                   Citric acid, sufficient for                                                                         pH = 5                                                  Water, sufficient for 100 g                                                   ______________________________________                                    

When applied to washed hair, this non-rinse product facilitates combingandpermits easy implementation of the permanent wave. It protects thehair andprolongs the hold of the waves.

EXAMPLE 7b

The following non-rinse lotion for use before a permanent is prepared:

    ______________________________________                                        Trimethylcetylammonium bromide                                                                         0.15 g                                               Compound of Example VIIb 2.2 g                                                Perfume                  0.2 g                                                Dyes                     0.01 g                                               Citric acid, sufficient for                                                                            pH = 4                                               Water, sufficient for    100 g                                                ______________________________________                                    

When applied to washed hair, this non-rinse product facilitates combingandpermits easy implementation of the permanent. It protects the hairand prolongs the hold of the wave.

EXAMPLE 8a

The following permanent wave composition is prepared:

    ______________________________________                                        Reducing agent liquid                                                         Thioglycolic acid       3 g                                                   Thiolactic acid         2 g                                                   Ammonia, 22° Be  4 g                                                   Triethanolamine         3.5 g                                                 Compound of Example VIb 1.4 g                                                 Perfume                 0.2 g                                                 Dyes                    0.05 g                                                Water, sufficient for   100 g                                                 Fixing Agent Liquid                                                           Potassium bromate       9.5 g                                                 Cetylpyridinium chloride                                                                              1 g                                                   Tartaric acid, sufficient for                                                                         pH = 6.5                                              Perfume                 0.1 g                                                 Dyes                    0.05 g                                                Water, sufficient for   100 g                                                 ______________________________________                                    

On sensitized hair, the reducing agent liquid is applied very easily anditdeeply penetrates the hair. After rinsing and after application of thefixing agent liquid, a very strong and regular wave is attained. Thehair is in a very beautiful cosmetic state. After drying, the hair isvery softand particularly shiny. The hold of the hair style isparticularly good.

EXAMPLE 8b

The following permanent wave composition is prepared:

    ______________________________________                                        Reducing Agent Liquid                                                         Thioglycolic acid       3.5 g                                                 Thiolactic acid         2 g                                                   Ammonia, 22° Be  3.5 g                                                 Triethanolamine         4 g                                                   Compound of Example VIIIb                                                                             2 g                                                   Perfume                 0.2 g                                                 Dyes                    0.01 g                                                Water, sufficient for   100 g                                                 Fixing Agent Liquid                                                           Potassium bromate       8 g                                                   Cetylpyridinium chloride                                                                              0.8 g                                                 Tartaric acid, sufficient for                                                                         pH = 6.5                                              Perfume                 0.2 g                                                 Dyes                    0.05 g                                                Water, sufficient for   100 g                                                 ______________________________________                                    

On sensitized hair, the reducing agent liquid is applied easily and itpenetrates deeply into the hair. After rinsing and after application ofthe fixing agent liquid, a very strong and very regular wave isobtained. The hair is in a very beautiful cosmetic state. After drying,the hair is very soft and particularly shiny. The hold of the hair styleis particularly good.

What is claimed is:
 1. A crosslinked polymer, which is soluble in waterat 10 weight percent thereof without gel formation, obtained bycrosslinking a polyamino-polyamide with a crosslinking agent whereinsaid crosslinking agent is employed in an amount of 0.025 to 0.35 moleper amine group of said polyamino-polyamide, said polyamino-polyamidebeing prepared by the polycondensation of (a) an acidic compoundselected from the group consisting of (i) an acid selected from thegroup consistintg of an organic saturated dicarboxylic acid having from6 to 10 carbon atoms and terephthalic acid, (ii) the addition compoundof one mole of an alkylenediamine with two moles of an unsaturated acidselected from the group consisting of acrylic acid, methacrylic acid anditaconic acid, (iii) an ester of said compounds of (i) and (ii) with alower alkanol having 1-6 carbon atoms and (iv) mixtures of (i), (ii) and(iii) on (b) a polyamine selected from the group consisting ofbis-primary mono-secondary polyalkylene polyamine and bis-primarybis-secondary polyalkylene polyamine, said polyamine (b) beingreplaceable by a member selected from the group consisting of (1) up to20 mole percent hexamethylene diamine, (2) up to 40 mole percentbis-primary amine and (3) up to 40 mole percent bis-secondary amine,said crosslinking agent being selected from the group consisting of:(I)simple bi-functional compounds selected from the group consisting of (1)bis-halohydrins resulting from the reaction of an epihalohydrin with aprimary amine, a bis-secondary diamine, a bis-phenol or a bis-mercaptan,(2) a bis-azetidinium derived from N,N-dialkyl halogeno hydroxypropylamine by cyclization or from bis-halohydrin for which thehalohydrin units are linked to the remainder of the molecule by tertiarynitrogen groups, and carry two azetidinium groups or one azetidiniumgroup and one halohydrin group, (3) a bis-haloacyl diamine, and (4) analkyl bis-halide of the formula ##STR35## wherein X=Cl or Br, Zrepresents ##STR36## x=1 to 3, m=0 or 1, n=0 or 1, m and n do notrepresent 1 at the same time, with the proviso that when m=1, x=1, A₁represents a saturated divalent hydrocarbon radical having 2,3,4 or 6carbon atoms or 2-hydroxyl propylene; (II) an oligomer obtained by thereaction of compound (a) selected from the group consisting of compounds(1), (2), (3) and (4), each defined above, (5) an epihalohydrin, (6) abis-epoxide and (7) a bis-unsaturated derivative, with a compound (b)which is a bi-functional compound reactive with said compound (a), saidcompound (b) being selected from the group consisting of primary amine,a bis-secondary diamine, a bis-mercaptan and a bis-phenol, the molarratio of (b):(a) being between 0.1 and 0.9; (II-bis) an oligomerobtained by the reaction of compound (a₁) selected from the groupconsisting of compounds (1), (3), (4) and (6) each defined above, with abis-tertiary diamine (b₁) which is a bi-functional compound reactivewith said compound (a₁), the molar ratio of (b₁):(a₁) being between 0.1and 0.9; (III) the quaternization product of compound (a₂) selected fromthe group consisting of (1) a bis-halohydrin resulting from the reactionof an epihalohydrin with piperizine, a bis-phenol or a bis-mercaptan;(2) a bis-azetidinum, defined above in (I) (2), (3) a bis-haloacyldiamine, (4) an alkyl bis-halide of formula F₁ above, (6) a bis-epoxide,(7) a bis-unsaturated derivative, (8) an oligomer II obtained by thereaction of compound (a₃) selected from the group consisting ofcompounds (1), (2), (3), (4), (6) and (7) each defined above with acompound (b₃) which is a bi-functional compound reactive with saidcompound (a₃), said compound (b₃) being selected from the groupconsisting of a primary amine, a bis-secondary diamine, a bis-mercaptanand a bis-phenol, the molar ratio of (b₃):(a₃) being between 0.1 and0.9; (9) an oligomer obtained by the reaction of an epihalohydrin (a₄)with a compound (b₄) which is a bi-functional compound reactive withsaid compound (a₄), said compound (b₄) being selected from the groupconsisting of piperazine, a bis-mercaptan, a bis-phenol and abis-epoxide of piperazine, the molar ratio of (b₄):(a₄) being between0.1 and 0.9, and (10) an oligomer obtained by the reaction of a compound(a₅) selected from the group consisting of (1) a bis-halohydrinresulting from the reaction of an epihalohydrin with piperazine, abis-phenol or a bis-mercaptan, (2) a bis-halocyl diamine, (3) an alkylbis-halide of formula F₁ above and (4) a bis-epoxide, with a compound(b₅), said compound (b₅) being a bis-tertiary diamine, the molar ratio(b₅):(a₅) being between 0.1 and 0.9; and said product having a tertiaryamine group alkylated with an alkylating agent (c) selected from thegroup consisting of methyl or ethyl chloride, bromide, iodide, sulfate,mesylate and tosylate, benzyl chloride or bromide, ethylene oxide,propylene oxide and glycidol.
 2. The polymer of claim 1 wherein saidacidic compound employed in preparing said polyaminopolyamide isselected from the group consisting of adipic acid, terephthalic acid,the dimethyl ester of said acids and the addition product ofethylenediamine on acrylic acid, methacrylic acid or itaconic acid, ortheir methyl esters.
 3. The polymer of claim 1 wherein the polyamineemployed in preparing said polyamino-polyamide is selected from thegroup consisting of diethylene triamine, dipropylene triamine,triethylene tetramine and a mixture of any one thereof with one or moreof ethylene diamine, hexamethylene diamine and piperazine.
 4. Thepolymer of claim 1 wherein said polyaminopolyamide is obtained by thecondensation of adipic acid on diethylene triamine.
 5. The polymer ofclaim 1 wherein said crosslinking agent is employed in an amount of0.025 to about 0.2 mole per amine group of said polyamino-polyamide. 6.The polymer of claim 1 wherein said crosslinking agent is employed in anamount of 0.025 to about 0.1 mole per amine group of saidpolyamino-polyamide.
 7. The polymer of claim 1 wherein said crosslinkingagent is selected from the group consisting ofa bis halohydrin selectedfrom the group consisting of ##STR37## (5) X--CH₂ --CHOH--CH₂ O--CH₂--CH₂ --O--_(p) CH₂ --CHOH--CH₂ X wherein p=0-25, ##STR38## and (7)X--CH₂ --CHOH--CH₂ --S--(CH₂)_(q) --S--CH₂ --CHOH--CH₂ X, wherein q=2-6,and X in (1)-(7) above represents Cl or Br; a bis-azetidinium of theformula ##STR39## a bis-haloacyl diamine of the formula (9) ##STR40##wherein X=Cl or Br, A=--CH₂ --CH₂ --, --CH₂ --CH₂ --CH₂ -- or ##STR41##n=1-10, R₁ =R₂ =hydrogen or R₁ and R₂ linked together representethylene; when ##STR42## R₁ and R₂ represent hydrogen; when A=--CH₂--CH₂ --, R₁ and R₂ can be linked together and represent ethylene withthe group ##STR43## and an alkyl bis-halide of the formula ##STR44##wherein X=Cl or Br, Z represents ##STR45## x=1-3, m=0 or 1, n=0 or 1, mand n not representing 1 at the same time, when m=1, x=1, and A₁represents a divalent hydrocarbon radical having 2, 3, 4 or 6 carbonatoms or 2-hydroxy propylene.
 8. The polymer of claim 1 wherein thebi-functional reactive compound (b) in crosslinking agent (II) isselected from the group consisting of a primary amine, a bis-secondarydiamine and a bis-mercaptan.
 9. The polymer of claim 1 wherein thebi-functional reactive compound (b) in crosslinking agent (II) isselected from the group consisting of piperazine and 1,2-dithiol ethane.10. The polymer of claim 1 wherein compound (a) in crosslinking agent(II) is selected from the group consisting of (1) a bis-halohydrinresulting from the reaction of an epihalohydrin with a primary amine, abis-secondary diamine, a bis-phenol or a bis-mercaptan, (2) abis-azetidinium defined in (I)(2), (3) a bis-haloacyl diamine, (4) analkyl bis-halide of the formula ##STR46## wherein X=Cl or Br, Zrepresents ##STR47## x=1-3, m=0 or 1, n=0 or 1, m and n not representing1 at the same time, when m=1, x=1; A₁ represents a saturated divalenthydrocarbon radical having 2, 3, 4 or 6 carbon atoms or 2-hydroxypropylene, (5) an epihalohydrin, and (6) a bis-epoxide andthe compound(b) is a bis-phenol.
 11. The polymer of claim 10 wherein compound (b) isbis-phenol A or 2,2-(4,4'-dihydroxy diphenyl) propane.
 12. The polymerof claim 1 wherein the bifunctional reactive compound (b₁) incrosslinking agent (II-bis) is a bis-tertiary diamine.
 13. The polymerof claim 12 wherein compound (b₁) is selected from the group consistingof N,N,N',N'-tetramethyl ethylene-, propylene-, butylene- orhexamethylene-diamine.
 14. The polymer of claim 1 wherein the alkylatingagent (c) is dimethyl sulfate.
 15. The polymer of claim 1 wherein saidbisazetidinium is derived from a bis-halohydrin wherein the halohydrinunits are linked to the remainder of the molecule by tertiary nitrogengroups, said bis-azetidinium carrying two azetidinium groups or oneazetidinium group and one halohydrin group.
 16. The polymer of claim 1wherein said crosslinking agent is selected from the group consisting of##STR48##
 17. The crosslinked polymer of claim 1 wherein up to 20 molepercent of said polyamine (b) is replaced by hexamethylene diamine. 18.The crosslinked polymer of claim 1 wherein up to 40 mole percent of saidpolyamine (b) is replaced by a ethylene diamine.
 19. The crosslinkedpolymer of claim 1 wherein up to 40 mole percent of said polyamine (b)is replaced by piperazine.
 20. A crosslinked polymer which is soluble inwater at 10 weight percent thereof without gel formation, obtained bycrosslinking a polyamino-polyamide with a crosslinking agent whereinsaid crosslinking agent is employed in an amount of 0.025 to 0.35 moleper amine group of said polyamino-polyamide, said polyamino-polyamidebeing prepared by the polycondensation of adipic acid on diethylenetriamine,said crosslinking agent being selected from the groupconsisting of: ##STR49##
 21. A crosslinked polymer which is soluble inwater at 10 percent thereof without gel formation, obtained bycrosslinking a polyamino-polyamide with a crosslinking agent whereinsaid crosslinking agent is employed in an amount of 0.025 to 0.35 moleper amine group of said polyamino-polyamide, said polyamino-polyamidebeing prepared by the polycondensation of an acidic compound selectedfrom the group consisting of adipic acid, terephthalic acid, thedimethyl ester of said acids and the addition product of one mole ofethylenediamine on two moles of acrylic acid, methacrylic acid oritaconic acid, or their methyl esters, on a polyamine selected from thegroup consisting of (i) diethylene triamine, (ii) dipropylene triamine,(iii) triethylene tetraamine and a mixture of any one of (i), (ii) and(iii) with one or more of ethylene diamine, hexamethylene diamine andpiperazine,said crosslinking agent being selected from the groupconsisting of: ##STR50##
 22. A crosslinked polymer, which is soluble inwater at 10 weight percent thereof without gel formation, obtained bycrosslinking a polyamino-polyamide with a crosslinking agent whereinsaid crosslinking agent is employed in an amount of 0.025 to 0.35 moleper amine group of said polyamino-polyamide, said polyamino-polyamidebeing prepared by the polycondensation of (a) an acidic compoundselected from the group consisting of (i) an acid selected from thegroup consisting of an organic saturated dicarboxylic acid having from 6to 10 carbon atoms and terephthalic acid, (ii) the addition compound ofone mole of an alkylenediamine with two moles of an unsaturated acidselected from the group consisting of acrylic acid, methacrylic acid anditaconic acid, (iii) an ester of said compounds of (i) and (ii) with alower alkanol having 1-6 carbon atoms and (iv) mixtures of (i), (ii) and(iii) on (b) a polyamine selected from the group consisting of abis-primary mono-secondary polyalkylene polyamine and a bis-primarybis-secondary polyalkylene polyamine, said polyamine (b) beingreplaceable by a member selected from the group consisting of (1) up to20 mole percent hexamethylene diamine, (2) up to 40 mole percentbis-primary amine and (3) up to 40 mole percent bis-secondary amine,said crosslinking agent being a bis-halohydrin having the formula##STR51## wherein n is 1-4 and X is Cl or Br.
 23. A crosslinked polymer,which is soluble in water at 10 weight percent thereof without gelformation, obtained by crosslinking a polyamino-polyamide with acrosslinking agent wherein said crosslinking agent is employed in anamount of 0.025 to 0.35 mole per amine group of saidpolyamino-polyamide, said polyamino-polyamide being prepared by thepolycondensation of (a) an acidic compound selected from the groupconsisting of (i) an acid selected from the group consisting of anorganic saturated dicarboxylic acid having from 6 to 10 carbon atoms andterephthalic acid, (ii) the addition compound of one mole of analkylenediamine with two moles of an unsaturated acid selected from thegroup consisting of acrylic acid, methacrylic acid and itaconic acid,(iii) an ester of said compounds of (i) and (ii) with a lower alkanolhaving 1-6 carbon atoms and (iv) mixtures of (i), (ii) and (iii) on (b)a polyamine selected from the group consisting of a bis-primarymono-secondary polyalkylene polyamine and a bis-primary bis-secondarypolyalkylene polyamine, said polyamine (b) being replaceable by a memberselected from the group consisting of (1) up to 20 mole percenthexamethylene diamine, (2) up to 40 mole percent bis-primary amine and(3) up to 40 mole percent bis-secondary amine, said crosslinking agentbeing a bis-halohydrin having the formula ##STR52## wherein X is Cl orBr.
 24. A crosslinked polymer, which is soluble in water at 10 weightpercent thereof without gel formation, obtained by crosslinking apolyamino-polyamide with a crosslinking agent wherein said crosslinkingagent is employed in an amount of 0.025 to 0.35 mole per amine group ofsaid polyamino-polyamide, said polyamino-polyamide being prepared by thepolycondensation of (a) an acidic compound selected from the groupconsisting of (i) an acid selected from the group consisting of anorganic saturated dicarboxylic acid having from 6 to 10 carbon atoms andterephthalic acid, (ii) the addition compound of one mole of analkylenediamine with two moles of an unsaturated acid selected from thegroup consisting of acrylic acid, methacrylic acid and itaconic acid,(iii) an ester of said compounds of (i) and (ii) with a lower alkanolhaving 1-6 carbon atoms and (iv) mixtures of (i), (ii) and (iii) on (b)a polyamine selected from the group consisting of a bis-primarymono-secondary polyalkylene polyamine and a bis-primary bis-secondarypolyalkylene polyamine, said polyamine (b) being replaceable by a memberselected from the group consisting of (1) up to 20 mole percenthexamethylene diamine, (2) up to 40 mole percent bis-primary amine and(3) up to 40 mole percent bis-secondary amine, said crosslinking agentbeing a bis-halohydrin having the formula ##STR53## wherein n is 2-6 andX is Cl or Br.
 25. A crosslinked polymer, which is soluble in water at10 weight percent thereof without gel formation, obtained bycrosslinking a polyamino-polyamide with a crosslinking agent whereinsaid crosslinking agent is employed in an amount of 0.025 to 0.35 moleper amine group of said polyamino-polyamide, said polyamino-polyamidebeing prepared by the polycondensation of (a) an acidic compoundselected from the group consisting of (i) an acid selected from thegroup consisting of an organic saturated dicarboxylic acid having from 6to 10 carbon atoms and terephthalic acid, (ii) the addition compound ofone mole of an alkylenediamine with two moles of an unsaturated acidselected from the group consisting of acrylic acid, methacrylic acid anditaconic acid, (iii) an ester of said compounds of (i) and (ii) with alower alkanol having 1-6 carbon atoms and (iv) mixtures of (i), (ii) and(iii) on (b) a polyamine selected from the group consisting of abis-primary mono-secondary polyalkylene polyamine and a bis-primarybis-secondary polyalkylene polyamine, said polyamine (b) beingreplaceable by a member selected from the group consisting of (1) up to20 mole percent hexamethylene diamine, (2) up to 40 mole percentbis-primary amine and (3) up to 40 mole percent bis-secondary amine,said crosslinking agent being a bis-halohydrin having the formula##STR54## wherein R=C_(n) H_(2n+1) wherein n=1-18 or --(CH₂ --CH₂--O--_(m) H wherein m is 1 or 2 and X is Cl or Br.
 26. A crosslinkedpolymer, which is soluble in water at 10 weight percent thereof withoutgel formation, obtained by crosslinking a polyamino-polyamide with acrosslinking agent wherein said crosslinking agent is employed in anamount of 0.025 to 0.35 mole per amine group of saidpolyamino-polyamide, said polyamino-polyamide being prepared by thepolycondensation of (a) an acidic compound selected from the groupconsisting of (i) an acid selected from the group consisting of anorganic saturated dicarboxylic acid having from 6 to 10 carbon atoms andterephthalic acid, (ii) the addition compound of one mole of analkylenediamine with two moles of an unsaturated acid selected from thegroup consisting of acrylic acid, methacrylic acid and itaconic acid,(iii) an ester of said compounds of (i) and (ii) with a lower alkanolhaving 1-6 carbon atoms and (iv) mixtures of (i), (ii) and (iii) on (b)a polyamine selected from the group consisting of a bis-primarymono-secondary polyalkylene polyamine and a bis-primary bis-secondarypolyalkylene polyamine, said polyamine (b) being replaceable by a memberselected from the group consisting of (1) up to 20 mole percenthexamethylene diamine, (2) up to 40 mole percent bis-primary amine and(3) up to 40 mole percent bis-secondary amine, said crosslinking agentbeing a bis halohydrin having the formula

    X--CH.sub.2 --CHOH--CH.sub.2 --O--CH.sub.2 --CH.sub.2 --O--.sub.p CH.sub.2 --CHOH--CH.sub.2 X

wherein p is 0-25 and X is Cl or Br.
 27. A crosslinked polymer, which issoluble in water at 10 weight percent thereof without gel formation,obtained by crosslinking a polyamino-polyamide with a crosslinking agentwherein said crosslinking agent is employed in an amount of 0.025 to0.35 mole per amine group of said polyamino-polyamide, saidpolyamino-polyamide being prepared by the polycondensation of (a) anacidic compound selected from the group consisting of (i) an acidselected from the group consisting of an organic saturated dicarboxylicacid having from 6 to 10 carbon atoms and terephthalic acid, (ii) theaddition compound of one mole of an alkylenediamine with two moles of anunsaturated acid selected from the group consisting of acrylic acid,methacrylic acid and itaconic acid, (iii) an ester of said compounds of(i) and (ii) with a lower alkanol having 1-6 carbon atoms and (iv)mixtures of (i), (ii) and (iii) on (b) a polyamine selected from thegroup consisting of a bis-primary mono-secondary polyalkylene polyamineand a bis-primary bis-secondary polyalkylene polyamine, said polyamine(b) being replaceable by a member selected from the group consisting of(1) up to 20 mole percent hexamethylene diamine, (2) up to 40 molepercent bis-primary amine and (3) up to 40 mole percent bis-secondaryamine, said crosslinking agent being a bis-halohydrin having the formula##STR55## wherein X is Cl or Br.
 28. A crosslinked polymer, which issoluble in water at 10 weight percent thereof without gel formation,obtained by crosslinking a polyamino-polyamide with a crosslinking agentwherein said crosslinking agent is employed in an amount of 0.025 to0.35 mole per amine group of said polyamino-polyamide, saidpolyamino-polyamide being prepared by the polycondensation of (a) anacidic compound selected from the group consisting of (i) an acidselected from the group consisting of an organic saturated dicarboxylicacid having from 6 to 10 carbon atoms and terephthalic acid, (ii) theaddition compound of one mole of an alkylenediamine with two moles of anunsaturated acid selected from the group consisting of acrylic acid,methacrylic acid and itaconic acid, (iii) an ester of said compounds of(i) and (ii) with a lower alkanol having 1-6 carbon atoms and (iv)mixtures of (i), (ii) and (iii) on (b) a polyamine selected from thegroup consisting of a bis-primary mono-secondary polyalkylene polyamineand a bis-primary bis-secondary polyalkylene polyamine, said polyamine(b) being replaceable by a member selected from the group consisting of(1) up to 20 mole percent hexamethylene diamine, (2) up to 40 molepercent bis-primary amine and (3) up to 40 mole percent bis-secondaryamine, said crosslinking agnet being a bis-halohydrin having the formula

    X--CH.sub.2 --CHOH--CH.sub.2 --S--(CH.sub.2).sub.q --S--CH.sub.2 --CHOH--CH.sub.2 X

wherein q is 2-6 and X is Cl or Br.
 29. A crosslinked polymer, which issoluble in water at 10 weight percent thereof without gel formation,obtained by crosslinking a polyamino-polyamide with a crosslinking agentwherein said crosslinking agent is employed in an amount of 0.025 to0.35 mole per amine group of said polyamino-polyamide, saidpolyamino-polyamide being prepared by the polycondensation of (a) anacidic compound selected from the group consisting of (i) an acidselected from the group consisting of an organic saturated dicarboxylicacid having from 6 to 10 carbon atoms and terephthalic acid, (ii) theaddition compound of one mole of an alkylenediamine with two moles of anunsaturated acid selected from the group consisting of acrylic acid,methacrylic acid and itaconic acid, (iii) an ester of said compounds of(i) and (ii) with a lower alkanol having 1-6 carbon atoms and (iv)mixtures of (i), (ii) and (iii) on (b) a polyamine selected from thegroup consisting of a bis-primary mono-secondary polyalkylene polyamineand a bis-primary bis-secondary polyalkylene polyamine, said polyamine(b) being replaceable by a member selected from the group consisting of(1) up to 20 mole percent hexamethylene diamine, (2) up to 40 molepercent bis-primary amine and (3) up to 40 mole percent bis-secondaryamine, said crosslinking agent being a bis-azetidinium of the formula##STR56##
 30. A crosslinked polymer, which is soluble in water at 10weight percent thereof without gel formation, obtained by crosslinking apolyamino-polyamide with a crosslinking agent wherein said crosslinkingagent is employed in an amount of 0.025 to 0.35 mole per amine group ofsaid polyamino-polyamide, said polyamino-polyamide being prepared by thepolycondensation of (a) an acidic compound selected from the groupconsisting of (i) an acid selected from the group consisting of anorganic saturated dicarboxylic acid having from 6 to 10 carbon atoms andterephthalic acid, (ii) the addition compound of one mole of analkylenediamine with two moles of an unsaturated acid selected from thegroup consisting of acrylic acid, methacrylic acid and itaconic acid,(iii) an ester of said compounds of (i) and (ii) with a lower alkanolhaving 1-6 carbon atoms and (iv) mixtures of (i), (ii) and (iii) on (b)a polyamine selected from the group consisting of a bis-primarymono-secondary polyalkylene polyamine and a bis-primary bis-secondarypolyalkylene polyamine, said polyamine (b) being replaceable by a memberselected from the group consisting of (1) up to 20 mole percenthexamethylene diamine, (2) up to 40 mole percent bis-primary amine and(3) up to 40 mole percent bis-secondary amine, said crosslinking agentbeing a bis-haloacyl diamine of the formula ##STR57## wherein X is Cl orBr, A is --CH₂ --CH₂ --, --CH₂ --CH₂ --CH₂ -- or ##STR58## n=1-10, R₁=R₂ =hydrogen or R₁ and R₂ linked together represent ethylene; when##STR59## R₁ and R₂ represent hydrogen; when A=--CH₂ --CH₂ --, R₁ and R₂can be linked together and represent ethylene with the group ##STR60##31. A crosslinked polymer, which is soluble in water at 10 weightpercent thereof without gel formation, obtained by crosslinking apolyamino-polyamine with a crosslinking agent wherein said crosslinkingagent is employed in an amount of 0.025 to 0.35 mole per amine group ofsaid polyamino-polyamide, said polyamino-polyamide being prepared by thepolycondensation of (a) an acidic compound selected from the groupconsisting of (i) an acid selected from the group consisting of anorganic saturated dicarboxylic acid having from 6 to 10 carbon atoms andterephthalic acid, (ii) the addition compound of one mole of analkylenediamine with two moles of an unsaturated acid selected from thegroup consisting of acrylic acid, methacrylic acid and itaconic acid,(iii) an ester of said compounds of (i) and (ii) with a lower alkanolhaving 1-6 carbon atoms and (iv) mixtures of (i), (ii) and (iii) on (b)a polyamine selected from the group consisting of bis-primarymono-secondary polyalkylene polyamine and bis-primary bis-secondarypolyalkylene polyamine, said polyamine (b) being replaceable by a memberselected from the group consisting of (1) up to 20 mole percenthexamethylene diamine, (2) up to 40 mole percent bis-primary amine and(3) up to 40 mole percent bis-secondary amine, said crosslinking agentbeing an alkyl bis-halide of the formula ##STR61## wherein X=Cl or Br, Zrepresents ##STR62## x=1-3, m=0 or 1, n=0 or 1, m and n not representing1 at the same time, when m=1, x=1, and A₁ represents a divalenthydrocarbon radical having 2, 3, 4 or 6 carbon atoms or 2-hydroxypropylene.
 32. A crosslinked polymer obtained by crosslinking apolyamino-polyamide with a crosslinking agent, said polyamino-polyamidebeing prepared by the polycondensation of equimolar amounts of adipicacid and diethylene triamine, said polyamino-polyamide characterized bythe following unit

    --OC-(CH.sub.2).sub.4 --CONH--(CH.sub.2 --CH.sub.2 --NH.sub.2).sub.2 --

and said crosslinking agent being obtained by the reaction of piperazinebis-acrylamide and piperazine in molar proportions of 3/2 and having theformula ##STR63##
 33. A crosslinked polymer obtained by crosslinking apolyamino-polyamide with a crosslinking agent, said polyamino-polyamidebeing prepared by the polycondensation of equimolar amounts of adipicacid and diethylene triamine, said polyamino-polyamide characterized bythe following unit

    --OC--(CH.sub.2).sub.4 --CONH--(CH.sub.2 --CH.sub.2 --NH.sub.2).sub.2 --

and said crosslinking agent being obtained by the reaction ofepichlorohydrin and piperazine in molar proportions of 5/4 and havingthe formula ##STR64## where n=4.
 34. A crosslinked polymer obtained bycrosslinking a polyamino-polyamide with a crosslinking agent, saidpolyamino-polyamide being prepared by the polycondensation of equimolaramounts of adipic acid and diethylene triamine, said polyamino-polyamidecharacterized by the following unit

    --OC--(CH.sub.2).sub.4 --CONH--(CH.sub.2 --CH.sub.2 --NH.sub.2).sub.2 --

and said crosslinking agent having the formula ##STR65##
 35. Acrosslinked polymer obtained by crosslinking a polyamino-polyamide witha crosslinking agent, said polyamino-polyamide being prepared by thepolycondensation of equimolar amounts of adipic acid and diethylenetriamine, said polyamino-polyamide characterized by the following unit

    --OC--(CH.sub.2).sub.4 --CONH--(CH.sub.2 --CH.sub.2 --NH.sub.2).sub.2 --

and said crosslinking agent having the formula ##STR66##
 36. Acrosslinked polymer obtained by crosslinking a polyamino-polyamide witha crosslinking agent, said polyamino-polyamide being prepared by thepolycondensation of equimolar amounts of adipic acid and diethylenetriamine, said polyamino-polyamide characterized by the following unit

    --OC--(CH.sub.2).sub.4 --CONH--(CH.sub.2 --CH.sub.2 --NH.sub.2).sub.2 --

and said crosslinking agent having the formula ##STR67##
 37. Acrosslinked polymer obtained by crosslinking a polyamino-polyamide witha crosslinking agent, said polyamino-polyamide with a crosslinkingagent, said polyamino-polyamide being prepared by the polycondensationof equimolar amounts of adipic acid and diethylene triamine, saidpolyamino-polyamide characterized by the following unit

    --OC--(CH.sub.2).sub.4 --CONH--(CH.sub.2 --CH.sub.2 --NH.sub.2).sub.2 --

and said crosslinking agent being obtained by the reaction ofepichlorohydrin and piperazine in molar proportions of 4/3 and havingthe formula ##STR68##
 38. A crosslinked polymer obtained by crosslinkinga polyamino-polyamide with a crosslinking agent, saidpolyamino-polyamide being prepared by the polycondensation of equimolaramounts of adipic acid and diethylene triamine, said polyamino-polyamidecharacterized by the following unit --OC--(CH₂)₄ --CONH--(CH₂ --CH₂--NH₂)₂ -- and said crosslinking agent being obtained by the reaction ofepichlorohydrin and piperazine in molar proportions of 3/2 and havingthe formula ##STR69##